CN112226254B - Method for cooperatively treating waste circuit board and printing and dyeing wastewater - Google Patents

Method for cooperatively treating waste circuit board and printing and dyeing wastewater Download PDF

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CN112226254B
CN112226254B CN202011023964.XA CN202011023964A CN112226254B CN 112226254 B CN112226254 B CN 112226254B CN 202011023964 A CN202011023964 A CN 202011023964A CN 112226254 B CN112226254 B CN 112226254B
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waste circuit
circuit board
printing
coal
dyeing wastewater
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CN112226254A (en
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黄河
孙宁
周志江
肖菊
吴健
郑小伦
陈锋
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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
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • 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
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
    • 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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/09—Details of the feed, e.g. feeding of spent catalyst, inert gas or halogens
    • C10J2300/0903—Feed preparation

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention discloses a method for cooperatively treating waste circuit boards and printing and dyeing wastewater, which comprises the following steps: (1) Crushing the waste circuit board to obtain waste circuit board powder, and carrying out pretreatment; (2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, and uniformly mixing and stirring to obtain coal water slurry; (3) And (3) feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 6-10 s at the temperature of 1100-1500 ℃ and the pressure of 0.8-4.0 MPa to obtain synthesis gas and slag. The invention prepares the waste circuit board and the printing and dyeing wastewater into the water-coal-slurry, and after the water-coal-slurry is gasified, the carbon and hydrogen elements in the waste are changed into CO and H 2 The synthetic gas can be further utilized as fuel, liquid slag generated in the gasification process forms glassy slag after quenching and solidification, and harmful substances such as heavy metal and the like which are difficult to degrade are wrapped in the glassy slag, so that the resource utilization and harmless treatment of wastes are realized.

Description

Method for cooperatively treating waste circuit board and printing and dyeing wastewater
Technical Field
The invention relates to the technical field of waste treatment, in particular to a method for cooperatively treating waste circuit boards and printing and dyeing wastewater.
Background
With the development of science and technology, the updating and upgrading speed of electronic products is continuously accelerated, a large amount of electronic wastes are brought by the change of a large amount of electronic and electrical products, and waste circuit boards are the most important electronic wastes as core components of the electronic products. The waste circuit board is a mixture of glass fiber reinforced resin and a plurality of metals, and because the waste circuit board contains more substances and has a complex separation and decomposition process, the waste circuit board has certain difficulty in recycling treatment due to the characteristics. At present, the waste circuit board recovery processing method generally adopts a direct burying method, an incineration method, water washing, cracking and other methods, but toxic substances are released in the processing process, so that serious secondary pollution to the environment such as air or soil is easily caused.
The waste and coal are prepared into coal water slurry, and then the coal water slurry is treated by the coal water slurry gasification furnace in a synergic way, so that carbon and hydrogen elements in the waste can be changed into CO and H 2 And the like, and simultaneously, harmful substances in the waste are decomposed or solidified into the glassy state slag, so that the thorough cleanness and the maximum resource utilization of the waste treatment are realized, 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, the publication No. CN106433822B of "a coal water slurry of gasified coal blended with petrochemical waste and a pulping process thereof" in chinese patent literature includes coal, petrochemical waste, additives and water, wherein the petrochemical waste accounts for 0 to 6% but not zero of the total mass of the coal water slurry, and the additive is added in an amount of 0 to 1.5% but not zero of the total mass of dry coal.
However, because the content of metals such as copper in the waste circuit board is high, the combustion efficiency of the coal water slurry can be reduced when the waste circuit board is used for preparing the coal water slurry; and metal ions are easily introduced into the coal water slurry, and the existence of the metal ions can compress an electric double layer on the surface of coal, weaken electrostatic repulsion among coal particles, and enable the coal particles to easily agglomerate, so that the prepared coal water slurry has poor dispersibility and stability.
Disclosure of Invention
The invention aims to overcome the defects that the content of metal in the waste circuit board is high in the prior art, and the combustion efficiency of the coal water slurry can be reduced when the waste circuit board is mixed with coal to prepare the coal water slurry for synergistic treatment; and metal ions are easily introduced into the coal water slurry, so that coal particles are easily agglomerated, and the problem of poor dispersibility and stability of the prepared coal water slurry is caused.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit board to obtain waste circuit board powder, and carrying out pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additives into the printing and dyeing wastewater, and uniformly mixing and stirring to obtain coal water slurry;
(3) Feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 6-10 s at the temperature of 1100-1500 ℃ and the pressure of 0.8-4.0 MPa.
Preferably, the pretreatment method in the step (1) is as follows: adding sulfuric acid and hydrogen peroxide into the waste circuit board powder, and stirring and reacting for 1-3 h at 40-60 ℃.
Preferably, the concentration of the sulfuric acid is 5-6 mol/L, the mass concentration of the hydrogen peroxide is 20-30%, and the adding proportion of the waste circuit board powder to the sulfuric acid and the hydrogen peroxide is as follows: 1g: (40-50 mL): (8-10 mL).
Preferably, in the step (1), the waste circuit board is crushed and then screened by a 60-80-mesh sieve to obtain waste circuit board powder.
Preferably, the preparation method of the additive in the step (2) comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water, and stirring for 30-40 min to obtain a mixed solution; heating to 75-85 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, keeping the temperature, reacting for 5-6 h, cooling to below 50 ℃, and adjusting the pH value to 6-7 by using a sodium hydroxide solution to obtain the additive.
Preferably, the mol ratio of the allyl polyoxyethylene ether, the acrylic acid, the sodium 2-acrylamide-2-methylpropanesulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid is 1: (1.5-2): (0.4-0.6): (1.5-2), the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 35-45% of the mass of the mixed solution.
Preferably, the mass of the ammonium persulfate in the added ammonium persulfate solution is 10 to 15% of the mass of the mixed solution.
Preferably, the allyl polyoxyethylene ether has a molecular weight of 1600 to 2400.
Preferably, the mass ratio of the waste circuit board powder, the coal powder, the additive and the printing and dyeing wastewater in the step (2) is (35-70): (100-200): 1: (60 to 150).
Preferably, the particle size of the pulverized coal in the step (2) is less than or equal to 1mm, the mixing and stirring speed is 300-600 rpm, and the stirring time is 5-20 min.
The invention pretreats the waste circuit board, mixes the waste circuit board with coal dust to prepare coal water slurry, gasifies the coal water slurry, and after the coal water slurry is gasified, carbon and hydrogen elements in the waste are changed into CO and H 2 The synthetic gas is an important raw material for chemical synthesis processes of synthetic ammonia, synthetic methanol and the like, can be further recycled, liquid slag generated in the gasification process forms glassy slag after being quenched and solidified, and harmful substances which are difficult to degrade such as heavy metals and the like are wrapped in the glassy slag, so that harmless treatment is realized.
In order to improve the performance of the prepared coal water slurry, the invention adopts the compounding of printing and dyeing wastewater, waste circuit boards and coal powder when preparing the coal water slurry. The printing and dyeing wastewater is one of the industrial wastewater with the largest discharge in China, and is difficult to treat due to strong alkalinity, high content of refractory organic matters such as dyes and the like. Because the printing and dyeing wastewater contains a large amount of surface active substances, the printing and dyeing wastewater can disperse the coal dust and improve the dispersibility of the coal water slurry, the printing and dyeing wastewater, the waste circuit boards and the coal dust are mixed to prepare the coal water slurry, and the performance of the coal water slurry is improved; meanwhile, the preparation of the coal water slurry by using the printing and dyeing wastewater reduces the consumption of clean water in the preparation process of the coal water slurry, and realizes the resource utilization of waste.
In order to improve the combustion performance of the coal water slurry, the invention firstly uses sulfuric acid and hydrogen peroxide to pretreat the crushed waste circuit board, removes metal substances such as copper and the like in the waste circuit board, reduces the metal content in the waste circuit board, and ensures the combustion efficiency of the coal water slurry prepared subsequently. However, the pretreated waste circuit board can introduce a large amount of metal ions into the coal water slurry, so that a double electric layer on the surface of coal is compressed, electrostatic repulsion among coal particles is weakened, the coal particles are easy to agglomerate, and the prepared coal water slurry is poor in dispersibility and stability.
Therefore, the polycarboxylic acid additive with imidazole groups and polyether groups on side chains is prepared by copolymerization of allyl polyoxyethylene ether, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid monomers, the additive prepared by the method can be adsorbed on the surfaces of coal particles through a hydrophobic main chain after the additive is added into coal water slurry, and the carboxylic acid groups, the sulfonic acid groups and other hydrophilic groups can enhance electrostatic repulsion among the coal particles, so that agglomeration among the coal particles is avoided; ether bonds on the side chains can form hydrogen bonds with water molecules to form a hydrophilic three-dimensional film, so that the dispersion stability of the coal particles is improved; meanwhile, the imidazole group on the side chain of the additive can effectively complex Cu introduced by the pretreated waste circuit board 2+ The metal ions are subjected to plasma treatment, so that the phenomenon of double electric layers compression caused by the metal ions is avoided, and the dispersion performance of the system is further ensured; and the spatial structure formed by complexing the metal ions and the imidazole groups can enable coal particles to be mutually crosslinked, generate mechanical resistance to the precipitation of the particles, effectively prevent the precipitation of the particles, improve the dispersion stability of the system, and prepare the coal water slurry with good dispersibility, stability and combustion efficiency.
The invention adopts 4- (1H-imidazole-1-yl) -2-butenoic acid monomer to participate in copolymerization, can introduce carboxylic acid group while introducing imidazole group, improve the content of hydrophilic group, avoid the wrapping effect of the imidazole group and metal ions on the hydrophilic group after complexing to weaken the electrostatic repulsion among the hydrophilic groups, thereby influencing the dispersibility of the coal water slurry.
Therefore, the invention has the following beneficial effects:
(1) Waste circuit boards and printing and dyeing wastewater are prepared into water-coal-slurry, and after the water-coal-slurry is gasified, carbon and hydrogen elements in wastes are changed into CO and H 2 The synthetic gas can be further used as fuel, and liquid slag generated in the gasification process forms glassy slag after quenching solidification, and the glassy slag is heavyMetal and other harmful substances difficult to degrade are wrapped inside, so that resource utilization and harmless treatment of wastes are realized;
(2) The printing and dyeing wastewater contains a large amount of surface active substances, which can disperse the coal powder and improve the dispersibility of the coal water slurry, so that the printing and dyeing wastewater, the waste circuit boards and the coal powder are mixed to prepare the coal water slurry, and the performance of the coal water slurry is improved; meanwhile, the preparation of the coal water slurry by using the printing and dyeing wastewater reduces the consumption of clean water in the preparation process of the coal water slurry, and realizes the resource utilization of waste;
(3) Firstly, the crushed waste circuit board is pretreated by sulfuric acid and hydrogen peroxide, so that metal substances such as copper and the like in the waste circuit board are removed, the metal content in the waste circuit board is reduced, and the combustion efficiency of the prepared coal water slurry is improved;
(4) The addition agent with imidazole group on the side chain is added into the coal water slurry, so that metal ions introduced by the waste circuit board can be effectively complexed, and the dispersibility and stability of the coal water slurry are improved.
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 embodiment of the invention is nakedflower coal with the grain diameter less than or equal to 1 mm.
Example 1:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards with a 60-mesh sieve to obtain waste circuit board powder; adding 5.5mol/L sulfuric acid and 25wt% of hydrogen peroxide into the waste circuit board powder, wherein the adding proportion of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:45mL of: 9mL, stirring and reacting at 50 ℃ for 2h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder to the coal powder to the additive to the printing and dyeing wastewater is 40:142:1:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry;
the preparation method of the additive comprises the following steps: mixing the components in a molar ratio of 1:1.8:0.5:1.8, sequentially adding allyl polyoxyethylene ether (molecular weight 2000), acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water, and stirring for 35min to obtain a mixed solution, wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 40% of the mass of the mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring and carrying out heat preservation reaction for 5.5 hours, wherein the mass of ammonium persulfate in the added ammonium persulfate solution is 12% of that of the mixed solution; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive;
(3) Feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
Example 2:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards through a 80-mesh sieve to obtain waste circuit board powder; adding 5mol/L sulfuric acid and 20wt% hydrogen peroxide into the waste circuit board powder, wherein the adding ratio of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:50mL of: stirring and reacting at 10mL and 40 ℃ for 3h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder, the coal powder, the additive to the printing and dyeing wastewater is 35:100:1:60, mixing and stirring at the rotating speed of 300rpm for 20min to obtain coal water slurry;
the preparation method of the additive comprises the following steps: mixing the components in a molar ratio of 1:1.5:0.4:2, sequentially adding allyl polyoxyethylene ether (with the molecular weight of 1600), acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water, and stirring for 30min to obtain a mixed solution, wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 35% of the mass of the mixed solution; heating to 75 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under a stirring state, stirring, keeping the temperature, and reacting for 6 hours, wherein the mass of ammonium persulfate in the added ammonium persulfate solution is 10% of that of the mixed solution; cooling to below 50 ℃, and adjusting the pH to 6 by using a sodium hydroxide solution to obtain the additive;
(3) And feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 10s at the temperature of 1100 ℃ and the pressure of 4.0MPa to obtain synthesis gas.
Example 3:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards through a 60-mesh sieve to obtain waste circuit board powder; adding 6mol/L sulfuric acid and 30wt% of hydrogen peroxide into the waste circuit board powder, wherein the adding proportion of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:40mL of: stirring and reacting at the temperature of 8mL and 60 ℃ for 1h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder, the coal powder, the additive to the printing and dyeing wastewater is 70:200:1:150, mixing and stirring at the rotating speed of 600rpm for 5min to obtain coal water slurry;
the preparation method of the additive comprises the following steps: mixing a mixture of 1:2:0.6:1.5 adding allyl polyoxyethylene ether (molecular weight of 2400), acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water in sequence, and stirring for 30min to obtain a mixed solution, wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 45% of the mass of the mixed solution; heating to 85 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under a stirring state, stirring, keeping the temperature, and reacting for 5 hours, wherein the mass of ammonium persulfate in the added ammonium persulfate solution is 15% of that of the mixed solution; cooling to below 50 ℃, and adjusting the pH to 7 by using a sodium hydroxide solution to obtain the additive;
(3) Feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 6s at the temperature of 1500 ℃ and the pressure of 0.8MPa to obtain synthesis gas.
Comparative example 1:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards with a 60-mesh sieve to obtain waste circuit board powder;
(2) Adding waste circuit board powder, coal powder and an additive into the printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder to the coal powder to the additive to the printing and dyeing wastewater is 40:142:1:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry, wherein the additive is a naphthalene dispersant produced by Huainan chemical plants;
(3) And feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
Comparative example 2:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards through a 60-mesh sieve to obtain waste circuit board powder;
(2) Adding waste circuit board powder, coal powder and an additive into the printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder to the coal powder to the additive to the printing and dyeing wastewater is 40:142:1:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry, wherein the preparation method of the additive is the same as that in the embodiment 1;
(3) And feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
Comparative example 3:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards with a 60-mesh sieve to obtain waste circuit board powder; adding 5.5mol/L sulfuric acid and 25wt% of hydrogen peroxide into the waste circuit board powder, wherein the adding proportion of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:45mL of: 9mL, stirring and reacting at 50 ℃ for 2h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder to the coal powder to the additive to the printing and dyeing wastewater is 40:142:1:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry;
the preparation method of the additive comprises the following steps: mixing the components in a molar ratio of 1:1.8:0.5 of allyl polyoxyethylene ether (molecular weight 2000), acrylic acid and 2-acrylamide-2-sodium methylacrylsulfonate are sequentially added into deionized water and stirred for 35min to obtain a mixed solution, wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid and the 2-acrylamide-2-sodium methylacrylsulfonate accounts for 40% of the mass of the mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring and carrying out heat preservation reaction for 5.5 hours, wherein the mass of ammonium persulfate in the added ammonium persulfate solution is 12% of that of the mixed solution; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive;
(3) And feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
Comparative example 4:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards through a 60-mesh sieve to obtain waste circuit board powder; adding 5.5mol/L sulfuric acid and 25wt% of hydrogen peroxide into the waste circuit board powder, wherein the adding proportion of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:45mL of: 9mL, stirring and reacting at 50 ℃ for 2h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder to the coal powder to the additive to the printing and dyeing wastewater is 40:142:1:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry;
the preparation method of the additive comprises the following steps: mixing a mixture of 1:1.8:0.5:2.5, sequentially adding allyl polyoxyethylene ether (molecular weight 2000), acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water, and stirring for 35min to obtain a mixed solution, wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid, the 2-acrylamide-2-sodium methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 40% of the mass of the mixed solution; heating to 80 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under a stirring state, stirring, keeping the temperature, and reacting for 5.5 hours, wherein the mass of the ammonium persulfate in the added ammonium persulfate solution is 12% of that of the mixed solution; cooling to below 50 ℃, and adjusting the pH to 6.5 by using a sodium hydroxide solution to obtain the additive;
(3) Feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
Comparative example 5:
a method for cooperatively treating waste circuit boards and printing and dyeing wastewater comprises the following steps:
(1) Crushing the waste circuit boards, and then sieving the crushed waste circuit boards through a 60-mesh sieve to obtain waste circuit board powder; adding 5.5mol/L sulfuric acid and 25wt% of hydrogen peroxide into the waste circuit board powder, wherein the adding proportion of the waste circuit board powder to the sulfuric acid to the hydrogen peroxide is 1g:45mL of: 9mL, stirring and reacting at 50 ℃ for 2h for pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additive into printing and dyeing wastewater, wherein the mass ratio of the waste circuit board powder, the coal powder, the additive to the printing and dyeing wastewater is 40:142:2:101, mixing and stirring at the rotating speed of 500rpm for 10min to obtain coal water slurry, wherein the preparation method of the additive is the same as that in the embodiment 1;
(3) Feeding the coal water slurry into a gasification furnace, and carrying out gasification reaction for 8s at the temperature of 1300 ℃ and the pressure of 2.0MPa to obtain synthesis gas.
The performance indexes of the coal water slurries prepared in the above examples and comparative examples and the content of effective gas in the obtained synthesis gas were tested, and the results are shown in table 1.
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 measured using a Brookfield R/S-CC + type rheometer (C40 rotor) at a shear rate of 100S -1 Viscosity at room temperature.
The fluidity and stability (24 hour stability) of the slurry were observed using the following method, wherein the fluidity rating was defined as: the continuous flow is A; the discontinuous flow is B; the flow is C under the action of external force; completely no flow is D. The slurry stability rating is specified as: after standing for 24 hours (the same below), the slurry body is kept in an initial state, the solid-liquid distribution is uniform, and the phenomena of water separation and precipitation are avoided, namely A; slightly worse than grade A, a small amount of water precipitation and soft precipitation are shown as B; more water separation and soft precipitation exist, but the initial state can be restored again through stirring, namely C; a hard precipitate was produced which was not restored to the original state by stirring the slurry, D.
Table 1: and (5) testing the performance of the coal water slurry.
Figure BDA0002701575140000071
Figure BDA0002701575140000081
As can be seen from Table 1, the coal water slurry prepared by the method of the present invention in examples 1 to 3 has good fluidity and dispersion stability, high solid content, and high content of effective gas after combustion; in the comparative example 1, the waste circuit board is not pretreated, and a commercial naphthalene dispersant is adopted, so that the stability and the combustion efficiency of the coal water slurry are obviously reduced; in comparative example 2, the additive prepared in the invention is adopted, but the waste circuit board is not modified, so that the combustion efficiency of the coal water slurry is obviously reduced compared with that in example 1; the additives in the comparative examples 3 and 4 do not introduce imidazole groups or change the addition amount of 4- (1H-imidazole-1-yl) -2-butenoic acid monomers during copolymerization, so that the addition amount falls outside the range of the invention, and the dispersion stability of the coal water slurry is reduced; in comparative example 5, the amount of the additive was changed so as to be outside the range of the present invention, the viscosity of the coal-water slurry was remarkably increased, and the fluidity was decreased. The addition of the additive and the proportion of the additive can ensure that the coal water slurry has good fluidity, dispersion stability and combustion efficiency, and improve the service performance of the coal water slurry.
The trace elements of the synthesis gas obtained in the above examples and comparative examples were analyzed, and the results are shown in table 2.
Table 2: and analyzing the trace elements of the synthesis gas.
Figure BDA0002701575140000082
As can be seen from Table 2, by using the method of the invention to cooperatively treat the waste circuit boards and the printing and dyeing wastewater, the characteristic pollutants of sulfur, chlorine, fluorine and nitrogen in the gasification cooperative treatment process are far lower than the emission standard; volatile heavy metal pollutants are not easy to enter the synthesis gas and are far lower than the emission standard; the emission value of dioxin substances in high-temperature reducing atmosphere is far lower than the emission standard. Further proves that under the high-temperature reducing atmosphere, the gasification cooperative treatment can effectively reduce the pollutant emission.

Claims (8)

1. A method for cooperatively treating waste circuit boards and printing and dyeing wastewater is characterized by comprising the following steps:
(1) Crushing the waste circuit board to obtain waste circuit board powder, and carrying out pretreatment;
(2) Adding the pretreated waste circuit board powder, coal powder and additives into the printing and dyeing wastewater, and uniformly mixing and stirring to obtain coal water slurry; the preparation method of the additive comprises the following steps: sequentially adding allyl polyoxyethylene ether, acrylic acid, 2-acrylamide-2-sodium methylacrylsulfonate and 4- (1H-imidazole-1-yl) -2-butenoic acid into deionized water, and stirring for 30 to 40min to obtain a mixed solution; heating to 75-85 ℃, dropwise adding an ammonium persulfate solution into the mixed solution under the stirring state, stirring, keeping the temperature, reacting for 5-6 h, cooling to below 50 ℃, and adjusting the pH to 6-7 by using a sodium hydroxide solution to obtain the additive; the mol ratio of the allyl polyoxyethylene ether to the acrylic acid to the sodium 2-acrylamide-2-methylpropanesulfonate to the 4- (1H-imidazole-1-yl) -2-butenoic acid is 1: (1.5 to 2): (0.4 to 0.6): (1.5 to 2), wherein the total mass of the allyl polyoxyethylene ether, the acrylic acid, the sodium 2-acrylamide-2-methylacrylsulfonate and the 4- (1H-imidazole-1-yl) -2-butenoic acid accounts for 35 to 45 percent of the mass of the mixed liquid;
(3) Feeding the water coal slurry into a gasification furnace, and carrying out gasification reaction for 6 to 10s at the temperature of 1100 to 1500 ℃ and the pressure of 0.8 to 4.0 MPa.
2. The cooperative treatment method of the waste circuit board and the printing and dyeing wastewater as claimed in claim 1, wherein the pretreatment method in the step (1) comprises the following steps: adding sulfuric acid and hydrogen peroxide into the waste circuit board powder, and stirring and reacting for 1-3 hours at the temperature of 40-60 ℃.
3. The method for the cooperative treatment of the waste circuit board and the printing and dyeing wastewater as claimed in claim 2, wherein the concentration of sulfuric acid is 5-6 mol/L, the mass concentration of hydrogen peroxide is 20-30%, and the adding proportion of waste circuit board powder to sulfuric acid and hydrogen peroxide is as follows: 1g: (40 to 50mL): (8 to 10mL).
4. The method for the cooperative treatment of the waste circuit boards and the printing and dyeing wastewater as claimed in claim 1 or 2, wherein in the step (1), the waste circuit boards are crushed and then screened by a sieve of 60 to 80 meshes to obtain waste circuit board powder.
5. The method for the cooperative treatment of the waste circuit board and the printing and dyeing wastewater as claimed in claim 1, wherein in an ammonium persulfate solution added in an additive preparation process, the mass of ammonium persulfate is 10 to 15% of the mass of a mixed solution.
6. The method for cooperatively treating the waste circuit board and the printing and dyeing wastewater as claimed in claim 1, wherein the molecular weight of the allyl polyoxyethylene ether in the step (2) is 1600 to 2400.
7. The method for the cooperative treatment of the waste circuit board and the printing and dyeing wastewater according to claim 1, wherein the mass ratio of the waste circuit board powder, the pulverized coal, the additive and the printing and dyeing wastewater in the step (2) is (35 to 70): (100 to 200): 1: (60 to 150).
8. The method for the cooperative treatment of the waste circuit board and the printing and dyeing wastewater according to claim 1, wherein the particle size of the pulverized coal in the step (2) is less than or equal to 1mm, the mixing and stirring speed is 300 to 600rpm, and the stirring time is 5 to 20min.
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