CN114573264B - Surface plugging coating for solid waste coarse slag in coal chemical industry, and preparation method and application thereof - Google Patents

Surface plugging coating for solid waste coarse slag in coal chemical industry, and preparation method and application thereof Download PDF

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CN114573264B
CN114573264B CN202210192679.3A CN202210192679A CN114573264B CN 114573264 B CN114573264 B CN 114573264B CN 202210192679 A CN202210192679 A CN 202210192679A CN 114573264 B CN114573264 B CN 114573264B
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chemical industry
coal chemical
solid waste
slag
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CN114573264A (en
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吕生华
危得全
吴磊
高党国
任洋军
赵海锋
贾君
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Processing Of Solid Wastes (AREA)

Abstract

The invention discloses a surface plugging coating of solid waste coarse slag in coal chemical industry, a preparation method and application thereof, and the main problems of the preparation of concrete by using the solid waste coarse slag in coal chemical industry instead of broken stone are large water consumption, poor fluidity, low compressive strength and low flexural strength, which are caused by multiple pores on the surface of the solid waste coarse slag. The invention prepares the surface plugging coating of the coal chemical industry solid waste coarse slag formed by the scrap collagen colloid and the polymer crosslinking enhancer, can form a layer of plugging coating on the surface of the coal chemical industry solid waste coarse slag, and promotes the surface morphology of the coarse slag to be improved through the coating so as to eliminate the influence of surface pores, thereby achieving the effects of reducing water consumption and improving fluidity and strength. The treated solid waste coarse slag has the characteristics of slump retention, good fluidity and pumping performance and high strength when being used for preparing concrete, and has positive significance for large-scale utilization of waste resources in coal chemical industry and reduction of carbon emission.

Description

Surface plugging coating for solid waste coarse slag in coal chemical industry, and preparation method and application thereof
Technical Field
The invention belongs to the technical field of cement-based composite material preparation, and particularly relates to a surface plugging coating for solid waste coarse slag in coal chemical industry, and a preparation method and application thereof.
Background
The coal chemical industry solid waste is solid waste generated in the process of converting coal into chemical products such as fuel gas, methanol, glycol, fuel oil and the like, and can be morphologically divided into granular coarse slag, fine slag and powdery ash. At present, the large-scale recycling of the solid waste in the coal chemical industry becomes an important problem to be solved urgently, and the reason is that the solid waste in the coal chemical industry has huge yield, low interest rate and environmental pollution. The comprehensive utilization rate of the solid waste in the coal chemical industry is not more than 30%, so that searching a large-scale low-cost harmless solid waste recycling utilization way is an urgent technology at present.
The components and the properties of the coal chemical industry solid waste determine that the coal chemical industry solid waste is most suitable for preparing concrete, and coarse slag and fine slag ash can respectively replace broken stone, sand and fly ash to prepare the concrete. The method has the advantages that a large amount of sand and stone are consumed for preparing the concrete each year, the sand and stone mainly comes from mountain opening and stone breaking and sand collection from river channels at present, and a large amount of sand and stone exploitation causes great damage and pollution to the environment in order to meet the concrete required by various buildings and engineering construction, so that the method is a very significant thing if coal chemical industry solid wastes can be used for preparing the concrete.
In addition, china is a large country of leather production, only 30% of leather becomes useful leather products in the leather making process, and 70% of leather becomes waste scraps and the like. Therefore, the recycling of the waste scraps is also a difficult problem which is urgently needed to be solved at present. At present, the waste leather is mainly treated in modes of burying, burning and the like, so that not only is huge waste of resources caused, but also great environmental pollution is generated.
The ash residues and coarse residues in the solid waste of the coal chemical industry are widely researched to replace gel materials and aggregates, and the ash residues of the coal chemical industry are mainly used for replacing fly ash at present, and the dosage is less than 20%. However, when the large-quantity coal chemical industry solid waste coarse slag is used for preparing concrete, the problems of high water absorption, large water consumption, poor fluidity, low strength, poor volume stability, poor permeation resistance and the like exist, so that the coal chemical industry solid waste is mainly used for paving roadbeds and preparing goaf filling concrete materials with low mechanical property requirements. The large-scale application of the solid waste in the coal chemical industry in preparing conventional C30 and C40 concrete is relatively lacking at present.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a surface plugging coating for solid waste coarse slag in coal chemical industry, and a preparation method and application thereof, so as to solve the problems of high water absorption, large water consumption, poor fluidity and low strength of the solid waste coarse slag in coal chemical industry when the solid waste coarse slag in coal chemical industry is used for preparing concrete, and solve the defects of large-scale preparation of C30 and C40 concrete by using the solid waste in coal chemical industry.
In order to achieve the above purpose, the invention is realized by adopting the following technical scheme:
the invention discloses a preparation method of a plugging coating on the surface of solid waste coarse slag in coal chemical industry, which comprises the following steps:
step one, preparation of waste collagen colloidal solution
Adding 60-80 parts of waste leather powder, 0.01-0.03 part of alkaline protease and 10-13 parts of 10% sodium hydroxide solution into 120-160 parts of water, stirring and heating, then preserving heat, and then heating and preserving heat again to obtain waste leather collagen colloid solution;
step two, preparation of polymer crosslinking enhancer
28 to 33 parts of N-methylolacrylamide, 21 to 25 parts of hydroxyethyl acrylate, 10 to 14 parts of 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 5 to 7 parts of allyl-N- (2-aminoethyl) carbamate, 0.6 to 0.9 part of persulfate and 56 to 69 parts of water are added into a reactor, stirred and heated to form a mixed monomer solution;
dissolving 0.4-0.7 part of sulfite in 40-50 parts of water to form an initiator solution, then dripping the initiator solution into the mixed monomer solution, continuing stirring and preserving heat after dripping, and regulating the pH value to 6.5-7.0 by using a sodium hydroxide solution with the mass fraction of 40%, wherein the obtained product is a polymer crosslinking enhancer;
step three, preparation of plugging coating on surface of solid waste coarse slag in coal chemical industry
100-120 parts of waste leather collagen colloid solution and 60-80 parts of polymer crosslinking enhancer are uniformly mixed according to parts by weight, 20-25 parts of glutaraldehyde solution with the mass fraction of 50% are mixed and uniformly stirred, the mixture is added into 300-350 parts of coal chemical industry solid waste coarse slag, the mixture is stirred, the surface of the coal chemical industry solid waste coarse slag is subjected to crosslinking reaction to form gel, 50-80 parts of coal chemical industry solid waste slag is then mixed, stirring is continued, and the gel is coated on the surface of the coal chemical industry solid waste coarse slag after curing to form a plugging coating.
Preferably, in the first step, the waste leather powder is obtained by crushing waste leather scraps generated in the leather making process, the moisture content is 10-15%, and the grain size is 1-3 mm.
Preferably, in the first step, the temperature is kept for 3 to 4 hours after stirring and heating to 50 to 60 ℃, and then the temperature is again heated to 95 to 98 ℃ and kept for 2 to 3 hours.
Preferably, in the second step, the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate; the sulfite is sodium bisulfite or sodium sulfite.
Preferably, in the second step, the heating temperature is 40-50 ℃, the dripping time is 30-40 min, and the heat preservation time is 1-2 h; in the third step, the stirring time is 10-15 min.
Preferably, the number average and weight average relative molecular weights of the polymer crosslinking enhancer are 8.53-10.83 ten thousand and 11.39-13.62 ten thousand respectively, and the molecular weight dispersion coefficient is 1.34-1.59.
The invention also discloses a plugging coating on the surface of the coal chemical industry solid waste coarse slag prepared by the method.
The invention also discloses application of the surface plugging coating of the solid waste coarse slag in the coal chemical industry in preparing the solid waste C30 concrete and the C40 concrete in the coal chemical industry, wherein the preparation of the C30 concrete is as follows:
according to the mass portion, 335 portions of common 42.5 Portland cement, 40 portions of coal chemical industry ash, 544 portions of sand, 200 portions of coal chemical industry solid waste fine slag and 1116 portions of coal chemical industry solid waste coarse slag with a plugging coating are mixed and stirred uniformly to form a cement sand stone mixture; then, 142.5 parts of water, 6.75 parts of polycarboxylate superplasticizer and 22.50 parts of graphene oxide dispersion are uniformly mixed, added into the cement and gravel mixture and uniformly stirred to obtain C30 concrete;
the preparation of C40 concrete was as follows:
according to the parts by weight, 396 parts of common 42.5 Portland cement, 50 parts of coal chemical industry ash, 477 parts of sand, 210 parts of coal chemical industry solid waste fine slag and 1122 parts of coal chemical industry solid waste coarse slag with a sealing coating are uniformly mixed and stirred to form a cement and sand mixture; and then, 142.5 parts of water, 8.03 parts of polycarboxylate superplasticizer and 26.76 parts of graphene oxide dispersion are uniformly mixed, added into the cement and gravel mixture and uniformly stirred, so that the C40 concrete is obtained.
Preferably, the sand is river sand or quartz sand, and consists of continuous grading with the particle size of 3-5 mm; the coal chemical industry solid waste fine slag is formed by continuous grading with the grain diameter of 3-5 mm.
Preferably, the graphene oxide is a nano sheet layer, the thickness of the nano sheet layer is 0.6-1.4 nm, the plane size of the nano sheet layer is 210-430 nm, the mass fraction of the graphene oxide is 0.05%, the doping amount of the graphene oxide is 0.003% of the sum of the cement and the ash, and the oxidation degree of the graphene oxide is expressed as 30% by oxygen content.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a plugging coating on the surface of solid waste coarse slag in coal industry, which uses waste scraps as a main raw material, prepares collagen colloidal solution through enzymatic degradation and thermal decomposition, contains amino, carboxyl, hydroxyl and other active groups in a protein colloidal structure, and forms a sealing coating on the surface of the solid waste coarse slag in coal industry under the action of glutaraldehyde crosslinking agent; the prepared polymer crosslinking enhancer selects N-methylol acrylamide, hydroxyethyl acrylate, 2-vinyl-4, 6-diamino-1, 3, 5-triazine and allyl-N- (2-amino ethyl) carbamate monomer, so that N-methylol, hydroxyethyl, triazine ring amino and amino with great reactivity in the structure of the polymer crosslinking enhancer can form gel to generate curing effect under the action of glutaraldehyde, and can generate strong crosslinking reaction with carboxyl, amino and amido in protein colloid, thereby being capable of quickly curing and forming a firm coating plugging coating on the surface of coal chemical industry solid waste coarse slag; the surface appearance of the coarse slag is improved through the coating, the surface hole pores are plugged, the mixing water consumption and the water absorption rate are reduced, the fluidity, the strength and the durability of the prepared high-content coal chemical industry solid waste concrete are improved, and the influence of the porous structure on the surface of the coarse slag on the working performance and the mechanical performance of the prepared concrete is reduced and eliminated; meanwhile, the invention finds a large-scale resource utilization way for the waste scraps, and has very important significance for large-scale resource utilization of the waste scraps.
The invention also discloses application of the surface plugging coating of the coal chemical industry solid waste coarse slag in preparing the coal chemical industry solid waste C30 concrete and the C40 concrete, wherein the content of the coal chemical industry solid waste in the prepared C30 concrete and C40 concrete is more than 56% in the total weight, and the coal chemical industry solid waste belongs to high-content coal chemical industry solid waste concrete; the initial value of slump is greater than 260mm, and the slump value of 2 hours is greater than 240mm; a 2 hour slump loss of <40mm over time; the expansion degree diameter of the concrete is 450-500 mm after 2 hours; when the cured for 28 days, the compressive strength is more than or equal to 40MPa, the flexural strength is more than or equal to 5MPa, and the water penetration resistance height is less than 10mm.
Further, the mass fraction of the graphene oxide is 0.05%, the mixing amount of the graphene oxide is 0.003% of the sum of the cement and the ash, and the ultra-low mixing amount of the graphene oxide is used for reinforcing and toughening high-content coal chemical industry solid waste to prepare concrete, so that ten times of the mixing amount is reduced compared with the conventional mixing amount of 0.03%, and the effects of ultra-low mixing amount, ultra-low cost and ultra-high economic benefit are achieved.
Drawings
FIG. 1 is a schematic diagram of a preparation process and a part of a structure of a plugging coating formed by the waste dander collagen colloidal solution;
FIG. 2 is a schematic diagram of a process for preparing a plugging coating by using the polymer crosslinking enhancer and a part of the structure.
Detailed Description
In order that those skilled in the art will better understand the present invention, a technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in which it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, shall fall within the scope of the present invention.
It should be noted that the terms "first," "second," and the like in the description and the claims of the present invention and the above figures are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate such that the embodiments of the invention described herein may be implemented in sequences other than those illustrated or otherwise described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention provides a coal chemical industry solid waste coarse slag surface plugging coating, a preparation method and application thereof, wherein the preparation method comprises a preparation technology of the coal chemical industry solid waste coarse slag surface plugging coating and a preparation technology of high-content coal chemical industry solid waste concrete.
The invention discloses a preparation method of a plugging coating on the surface of solid waste coarse slag in coal chemical industry, which comprises the following steps of:
step one, preparing a waste collagen colloidal solution: 60 to 80 parts of waste skin powder, 0.01 to 0.03 part of alkaline protease and 10 to 13 parts of 10 percent sodium hydroxide solution are put into 120 to 160 parts of water, stirred and heated to 50 to 60 ℃ and then kept for 3 to 4 hours, then heated to 95 to 98 ℃ and kept for 2 to 3 hours, and the waste skin collagen colloid solution is obtained, and the chemical reaction process is shown in figure 1.
Step two, preparing a polymer crosslinking enhancer: 28 to 33 parts of N-methylolacrylamide, 21 to 25 parts of hydroxyethyl acrylate, 10 to 14 parts of 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 5 to 7 parts of allyl-N- (2-aminoethyl) carbamate, 0.6 to 0.9 part of persulfate and 56 to 69 parts of water are added into a reactor, stirred and heated to 40 to 50 ℃ to form a mixed monomer solution; 0.4 to 0.7 part of sulfite is dissolved in 40 to 50 parts of water to form an initiator solution, then the initiator solution is dripped into the mixed monomer solution for 30 to 40 minutes, stirring is continued after dripping is finished, the temperature is kept for 1 to 2 hours, the pH value of a product is regulated and controlled to be 6.5 to 7.0 by using a sodium hydroxide solution with the mass fraction of 40 percent, the obtained product is the polymer crosslinking enhancer, the solid content of the polymer crosslinking enhancer is about 40 percent, and the chemical reaction process is shown in figure 2.
The preparation method comprises the following steps:
the waste leather powder is obtained by crushing waste leather scraps generated in the leather making process, the water content is 10% -15%, and the grain diameter is 1-3 mm.
The enzyme activity of the protease is 20-40 mu/g, and the effective content is 96-99%.
The N-methylol acrylamide, the hydroxyethyl acrylate, the 2-vinyl-4, 6-diamino-1, 3, 5-triazine and the allyl-N- (2-amino ethyl) carbamate are all chemically pure, and the content is more than 98 percent.
The persulfate is any one of ammonium persulfate, sodium persulfate or potassium persulfate, and the chemical purity is higher than 98%.
The sulfite is any one of sodium bisulfite and sodium sulfite, and has chemical purity of more than 98 percent.
The polymer crosslinking enhancer has good fluidity, is dissolved in water in any proportion, has a pH value of 6.5-7.0, and has a number average and weight average relative molecular mass of 8.53-10.83 ten thousand and 11.39-13.62 ten thousand, and a molecular weight dispersion coefficient of 1.34-1.59.
Step three, preparing a plugging coating on the surface of the solid waste coarse slag in the coal chemical industry: 100-120 parts of the prepared waste leather collagen colloidal solution and 60-80 parts of the polymer crosslinking enhancer are uniformly mixed, 20-25 parts of glutaraldehyde solution with the mass fraction of 50% are mixed and uniformly stirred, then the mixture is added into 300-350 parts of coal chemical industry solid waste coarse slag in a drum-type stirrer, stirring is carried out for 10-15 min, amino, carboxyl and hydroxyl in the waste leather collagen colloidal solution and amino, hydroxyl, triazine ring and the like in the polymer crosslinking enhancer are subjected to crosslinking reaction to form gel under the action of glutaraldehyde in the stirring process, 50-80 parts of coal chemical industry solid waste slag are mixed, stirring is continued for 10-15 min, and a plugging coating is formed on the surface of the solid waste coarse slag by coating the solidified gel, and the result is shown in fig. 1 and 2.
The preparation method comprises the following steps:
the coal chemical industry solid waste coarse slag comprises the following main components: siO (SiO) 2 The content is 38.45 percent to 42.37 percent，Al 2 O 3 26.41 to 30.53 percent of Fe 2 O 3 11.62 to 13.83 percent of CaO, 10.76 to 12.81 percent of MgO, 3.68 to 4.93 percent of MgO, the particles of which are crushed, granulated and screened, the water content is less than 5 percent, the porosity in the crude slag is 25.67 to 36.65 percent, and the density is 2.2 to 2.4g/cm 3 The grain diameter is controlled to be 15-35 mm in continuous grading;
the main components of the coal chemical industry solid waste ash are as follows: siO (SiO) 2 The content of Al is 38.53-39.76 percent 2 O 3 The content of Fe is 25.37-28.82 percent 2 O 3 10.68 to 12.93 percent of CaO, 8.82 to 10.92 percent of MgO, 2.54 to 3.93 percent of MgO, the fineness of the sieve residue of the square hole sieve with 0.045mm is not more than 20 percent, the water demand is not more than 105 percent, the loss on ignition is not more than 5 percent, the water content is not more than 5 percent, and the sulfur trioxide content is not more than 3 percent.
The application of the surface plugging coating of the solid waste coarse slag in the coal chemical industry in preparing the solid waste C30 concrete and the C40 concrete in the coal chemical industry, wherein the preparation method of the C30 concrete comprises the following steps:
according to the mass portion, 335 portions of common 42.5 Portland cement, 40 portions of coal chemical industry ash, 544 portions of sand, 200 portions of coal chemical industry solid waste fine slag, 1116 portions of coal chemical industry solid waste coarse slag with a plugging coating, 142.5 portions of water, 6.75 portions of polycarboxylic acid water reducer with 8% content and 22.50 portions of graphene oxide dispersion liquid are added into a mixer to be uniformly stirred, and then the water, the polycarboxylic acid water reducer and the graphene oxide dispersion liquid are added into a cement sand stone mixture to be uniformly stirred to obtain C30 concrete for preparing a detection sample and curing.
The preparation method of the C40 concrete comprises the following steps: according to the mass portion, 396 portions of common 42.5 Portland cement, 50 portions of coal chemical industry ash, 477 portions of sand, 210 portions of coal chemical industry solid waste slag, 1122 portions of coal chemical industry solid waste slag with a plugging coating, 142.5 portions of water, 8.03 portions of polycarboxylic acid water reducer with 8% content and 26.76 portions of graphene oxide dispersion liquid are added into a mixer to be uniformly stirred, and then the water, the polycarboxylic acid water reducer and the graphene oxide dispersion liquid are added into a cement sand stone mixture to be uniformly stirred to obtain C40 concrete for preparing a detection sample and curing.
The preparation method of the concrete comprises the following steps:
the main components of the coal chemical industry solid waste ash are the same as those in the third step.
The main components of the coal chemical industry solid waste slag are as follows: siO (SiO) 2 The content is 38.15 to 39.34 percent, al 2 O 3 24.62 to 27.65 percent of Fe 2 O 3 10.13 to 12.27 percent of CaO, 8.68 to 10.54 percent of MgO, 2.36 to 3.82 percent of MgO, no more than 105 percent of water demand, no more than 5 percent of loss on ignition, no more than 5 percent of water content, no more than 3 percent of sulfur trioxide, and the grain diameter of the material is controlled to be 3 to 5mm of continuous grading.
The coal chemical industry solid waste coarse slag containing the plugging coating is prepared by the invention.
The sand is river sand or quartz sand and consists of continuous grading with the grain diameter of 3-5 mm.
The graphene oxide is a nano-sheet layer, the doping amount of the graphene oxide is 0.003% of the sum of the cement and the ash, the mass fraction is 0.05%, the oxidation degree of the graphene oxide is 30% expressed by oxygen content, the thickness of the nano-sheet layer is 0.6-1.4 nm, and the plane size of the nano-sheet layer is 210-430 nm.
Example 1
Step one, preparation of waste collagen colloidal solution
60 parts of waste skin powder, 0.01 part of alkaline protease and 10 parts of 10% sodium hydroxide solution are put into 120 parts of water, stirred and heated to 50 ℃ and then heat-preserved for 3 hours, and then heated to 95 ℃ and heat-preserved for 2 hours, so as to obtain the waste skin collagen colloid solution.
Step two, preparation of polymer crosslinking enhancer
28 parts of N-methylolacrylamide, 21 parts of hydroxyethyl acrylate, 10 parts of 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 5 parts of allyl-N- (2-amino ethyl) carbamate, 0.6 part of persulfate and 56 parts of water are added into a reactor, stirred and heated to 40 ℃ to form a mixed monomer solution; dissolving 0.4 part of sulfite in 40 parts of water to form an initiator solution, then dropwise adding the initiator solution into the mixed monomer solution for 30min, continuously stirring and preserving heat for 1h after the dropwise adding, regulating the pH value of a product to be 6.5 by using a sodium hydroxide solution with the mass fraction of 40%, wherein the obtained product is the polymer crosslinking enhancer, and the solid content of the polymer crosslinking enhancer is about 40%.
Step three, preparation of plugging coating on surface of solid waste coarse slag in coal chemical industry
100 parts of prepared waste leather collagen colloid solution and 60 parts of polymer crosslinking enhancer are uniformly mixed, 20 parts of glutaraldehyde solution with the mass fraction of 50% are mixed and uniformly stirred, then the mixture is added into 300 parts of coal chemical industry solid waste coarse slag in a drum-type stirrer, stirring is carried out for 10min, in the stirring process, amino, carboxyl and hydroxyl in the waste leather collagen colloid solution and amino, hydroxyl, triazine rings and the like in the polymer crosslinking enhancer are subjected to crosslinking reaction under the action of glutaraldehyde to form gel, 50 parts of coal chemical industry solid waste slag are mixed, stirring is continued for 10min, and the gel is coated on the surface of the solid waste coarse slag to form a plugging coating.
Preparation method of high-content coal chemical industry solid waste C30 and C40 concrete
The components of the C30 concrete comprise 335 parts of common 42.5 Portland cement, 40 parts of coal chemical industry ash, 544 parts of sand, 200 parts of coal chemical industry solid waste fine slag, 1116 parts of coal chemical industry solid waste coarse slag with a plugging coating, 142.5 parts of water, 6.75 parts of 8% polycarboxylic acid water reducer and 22.50 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%, wherein the preparation process comprises the steps of adding cement, ash, sand, broken stone and coal chemical industry solid waste coarse slag with the plugging coating into a half mixer for uniformly stirring, and then adding the water, the polycarboxylic acid water reducer and the graphene oxide dispersion liquid into a cement sand stone mixture for uniformly stirring after uniformly mixing to obtain the C30 concrete for preparing a detection sample and curing.
The components of the C40 concrete are 396 parts of Portland cement No. 42.5, 50 parts of coal chemical industry ash, 477 parts of sand, 210 parts of coal chemical industry solid waste fine slag, 1122 parts of coal chemical industry solid waste coarse slag with a plugging coating, 142.5 parts of water, 8.03 parts of a polycarboxylic acid water reducer with 8% content and 26.76 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%, wherein the preparation process comprises the steps of adding cement, ash, sand, broken stone and coal chemical industry solid waste coarse slag with the plugging coating into a half mixer for uniformly stirring, and then adding the water, the polycarboxylic acid water reducer and the graphene oxide dispersion liquid into a cement sand stone mixture for uniformly stirring after uniformly mixing to obtain the C40 concrete for preparing a detection sample and curing.
Example 2
Step one, preparation of waste collagen colloidal solution
80 parts of waste skin powder, 0.03 part of alkaline protease and 13 parts of 10% sodium hydroxide solution are put into 160 parts of water, stirred and heated to 60 ℃ and then heat-preserved for 4 hours, and then heated to 98 ℃ and heat-preserved for 3 hours, so as to obtain the waste skin collagen colloid solution.
Step two, preparation of polymer crosslinking enhancer
33 parts of N-methylolacrylamide, 25 parts of hydroxyethyl acrylate, 14 parts of 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 7 parts of allyl-N- (2-amino ethyl) carbamate, 0.9 part of persulfate and 69 parts of water are added into a reactor, stirred and heated to 50 ℃ to form a mixed monomer solution; dissolving 0.7 part of sulfite in 50 parts of water to form an initiator solution, then dropwise adding the initiator solution into the mixed monomer solution for 40min, continuously stirring and preserving heat for 2h after the dropwise adding, regulating the pH value of a product to 7.0 by using a sodium hydroxide solution with the mass fraction of 40%, wherein the obtained product is the polymer crosslinking enhancer, and the solid content of the polymer crosslinking enhancer is about 40%.
Step three, preparation of plugging coating on surface of solid waste coarse slag in coal chemical industry
120 parts of prepared waste leather collagen colloid solution and 80 parts of polymer crosslinking enhancer are uniformly mixed, 25 parts of glutaraldehyde solution with the mass fraction of 50% is mixed and uniformly stirred, then the mixture is added into 350 parts of coal chemical industry solid waste coarse slag in a drum-type stirrer, stirring is carried out for 15min, in the stirring process, amino, carboxyl and hydroxyl in the waste leather collagen colloid solution and amino, hydroxyl, triazine ring and the like in the polymer crosslinking enhancer are subjected to crosslinking reaction under the action of glutaraldehyde to form gel, then 80 parts of coal chemical industry solid waste ash slag are mixed, stirring is continued for 15min, and the gel is coated on the surface of the solid waste coarse slag to form a plugging coating.
Preparation method of high-content coal chemical industry solid waste C30 and C40 concrete
The components of the C30 concrete comprise 335 parts of common 42.5 Portland cement, 40 parts of coal chemical industry ash, 544 parts of sand, 200 parts of coal chemical industry solid waste fine slag, 1116 parts of coal chemical industry solid waste coarse slag with a plugging coating, 142.5 parts of water, 6.75 parts of 8% polycarboxylic acid water reducer and 22.50 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%, wherein the preparation process comprises the steps of adding cement, ash, sand, broken stone and coal chemical industry solid waste coarse slag with the plugging coating into a half mixer for uniformly stirring, and then adding the water, the polycarboxylic acid water reducer and the graphene oxide dispersion liquid into a cement sand stone mixture for uniformly stirring after uniformly mixing to obtain the C30 concrete for preparing a detection sample and curing.
The components of the C40 concrete are 396 parts of Portland cement No. 42.5, 50 parts of coal chemical industry ash, 477 parts of sand, 210 parts of coal chemical industry solid waste fine slag, 1122 parts of coal chemical industry solid waste coarse slag with a plugging coating, 142.5 parts of water, 8.03 parts of 8% content polycarboxylate water reducer, 26.76 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%, and the preparation process comprises the steps of adding cement, ash, sand, broken stone and coal chemical industry solid waste coarse slag with the plugging coating into a half mixer for uniform stirring, and then adding the water, the polycarboxylate water reducer and the graphene oxide dispersion liquid into a cement sand stone mixture for uniform stirring after uniformly mixing to obtain the C40 concrete for preparing a detection sample and curing.
The properties of the high-content coal chemical industry solid waste concrete in the examples are shown in Table 1 below.
Table 1 Properties of high content coal chemical industry solid waste concrete in examples
The comparative concrete samples in table 1 were prepared in the same manner as in the examples, except for the composition of the concrete, wherein the component proportions of the C30 concrete were: 375 parts of ordinary No. 42.5 Portland cement, 744 parts of sand, 1116 parts of crushed stone, 142.5 parts of water, 6.75 parts of 8% polycarboxylate superplasticizer and 22.50 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%.
The component proportion of the C40 concrete is as follows: 446 parts of common No. 42.5 Portland cement, 687 parts of sand, 1122 parts of crushed stone, 142.5 parts of water, 8.03 parts of 8% polycarboxylate superplasticizer and 26.76 parts of graphene oxide dispersion liquid with the mass fraction of 0.05%.
The detection method is carried out according to the national standard method.
The above is only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited by this, and any modification made on the basis of the technical scheme according to the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (8)

1. The preparation method of the plugging coating on the surface of the solid waste coarse slag in the coal chemical industry is characterized by comprising the following steps:
step one, preparation of waste collagen colloidal solution
Adding 60-80 parts of waste leather powder, 0.01-0.03 part of alkaline protease and 10-13 parts of 10% sodium hydroxide solution into 120-160 parts of water, stirring and heating to 50-60 ℃, then preserving heat for 3-4 hours, and then heating to 95-98 ℃ again and preserving heat for 2-3 hours to obtain waste leather collagen colloid solution;
step two, preparation of polymer crosslinking enhancer
28 to 33 parts of N-methylolacrylamide, 21 to 25 parts of hydroxyethyl acrylate, 10 to 14 parts of 2-vinyl-4, 6-diamino-1, 3, 5-triazine, 5 to 7 parts of allyl-N- (2-aminoethyl) carbamate, 0.6 to 0.9 part of persulfate and 56 to 69 parts of water are added into a reactor, stirred and heated to form a mixed monomer solution; the heating temperature is 40-50 ℃;
dissolving 0.4-0.7 part of sulfite in 40-50 parts of water to form an initiator solution, then dripping the initiator solution into the mixed monomer solution, continuing stirring and preserving heat after dripping, and regulating the pH value to 6.5-7.0 by using a sodium hydroxide solution with the mass fraction of 40%, wherein the obtained product is a polymer crosslinking enhancer; the dripping time is 30-40 min, and the heat preservation time is 1-2 h;
step three, preparation of plugging coating on surface of solid waste coarse slag in coal chemical industry
Mixing 100-120 parts of waste leather collagen colloid solution with 60-80 parts of polymer crosslinking enhancer in parts by mass, mixing 20-25 parts of glutaraldehyde solution with the mass fraction of 50%, stirring uniformly, adding into 300-350 parts of coal chemical industry solid waste coarse slag, stirring, performing crosslinking reaction on the surface of the coal chemical industry solid waste coarse slag to form gel, then mixing 50-80 parts of coal chemical industry solid waste slag, continuing stirring, and coating the gel after curing on the surface of the coal chemical industry solid waste coarse slag to form a plugging coating; wherein the stirring time is 10-15 min.
2. The method for preparing the plugging coating on the surface of the solid waste coarse slag in the coal chemical industry, which is characterized in that in the first step, the waste leather powder is obtained by crushing waste leather scraps generated in the leather making process, the moisture content is 10-15%, and the particle size is 1-3 mm.
3. The method for preparing the plugging coating on the surface of the solid waste slag in the coal chemical industry according to claim 1, wherein in the second step, the persulfate is ammonium persulfate, sodium persulfate or potassium persulfate; the sulfite is sodium bisulfite or sodium sulfite.
4. The method for preparing the plugging coating on the surface of the solid waste slag in the coal chemical industry according to claim 1, wherein the number average and weight average molecular weight of the polymer crosslinking enhancer are 8.53-10.83 ten thousand and 11.39-13.62 ten thousand respectively, and the molecular weight dispersion coefficient is 1.34-1.59.
5. A surface plugging coating of coal chemical industry solid waste coarse slag prepared by the method of any one of claims 1 to 4.
6. The application of the surface plugging coating of the solid waste slag in the coal chemical industry in preparing solid waste C30 concrete and C40 concrete in the coal chemical industry, which is characterized in that the preparation of the C30 concrete is as follows:
according to the mass portion, 335 portions of common 42.5 Portland cement, 40 portions of coal chemical industry ash, 544 portions of sand, 200 portions of coal chemical industry solid waste fine slag and 1116 portions of coal chemical industry solid waste coarse slag with a plugging coating are mixed and stirred uniformly to form a cement sand stone mixture; then, 142.5 parts of water, 6.75 parts of polycarboxylate superplasticizer and 22.50 parts of graphene oxide dispersion are uniformly mixed, added into the cement and gravel mixture and uniformly stirred to obtain C30 concrete;
the preparation of C40 concrete was as follows:
according to the parts by weight, 396 parts of common 42.5 Portland cement, 50 parts of coal chemical industry ash, 477 parts of sand, 210 parts of coal chemical industry solid waste fine slag and 1122 parts of coal chemical industry solid waste coarse slag with a sealing coating are uniformly mixed and stirred to form a cement and sand mixture; and then, 142.5 parts of water, 8.03 parts of polycarboxylate superplasticizer and 26.76 parts of graphene oxide dispersion are uniformly mixed, added into the cement and gravel mixture and uniformly stirred, so that the C40 concrete is obtained.
7. The use according to claim 6, wherein the sand is river sand or quartz sand, consisting of a continuous grading with a particle size of 3-5 mm; the coal chemical industry solid waste fine slag is formed by continuous grading with the grain diameter of 3-5 mm.
8. The use according to claim 6, wherein the graphene oxide is a nano-sheet layer, the thickness of the nano-sheet layer is 0.6-1.4 nm, the planar size of the nano-sheet layer is 210-430 nm, the mass fraction of the graphene oxide is 0.05%, the doping amount of the graphene oxide is 0.003%, and the oxidation degree of the graphene oxide is expressed as 30% by oxygen content.
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