CN116161912A - Preparation method of oil-absorbing composite cementing material and floating block for absorbing greasy dirt on water surface - Google Patents
Preparation method of oil-absorbing composite cementing material and floating block for absorbing greasy dirt on water surface Download PDFInfo
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- CN116161912A CN116161912A CN202310209461.9A CN202310209461A CN116161912A CN 116161912 A CN116161912 A CN 116161912A CN 202310209461 A CN202310209461 A CN 202310209461A CN 116161912 A CN116161912 A CN 116161912A
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
-
- 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
- C04B2111/00017—Aspects relating to the protection of the environment
-
- 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)
- Organic Chemistry (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention provides a preparation method of an oil-absorbing composite cementing material, which comprises cement, fly ash, slag, shell powder, polyethylene glycol, silane impregnant and fiber, wherein the fly ash, the slag and strong alkali are utilized to modify the shell powder so as to construct an oil-absorbing pore canal inside a cement-based cementing material; adopting silane impregnant, high molecular weight polyethylene glycol and modified fiber to adjust the polarity of the inside of the cement-based glue material pores so as to enable the surfaces of particles in the pores to show oil wettability; the surface of the cement-based adhesive material is coated with the silane impregnant to form a hydrophobic layer, so that the surface layer of the cement-based adhesive material is converted from typical hydrophilic property to hydrophobic property, and the hydrophobic and oleophylic effects are achieved. The volume oil absorption of the oil-absorbing composite cementing material is more than 4 times that of the traditional cementing material, and the oil-absorbing floating block is prepared by adopting the shell cement oil-absorbing composite cementing material to bond ceramsite coarse aggregate, has good floatability on water surface and can be recycled, so that the oil-absorbing floating block can effectively absorb oil on water surface.
Description
Technical Field
The invention belongs to the technical field of water surface oil stain treatment, and particularly relates to a preparation method of an oil-absorbing composite cementing material and a water surface oil stain-absorbing floating block manufactured by using the oil-absorbing composite cementing material.
Background
In recent years, with the continuous exploitation and utilization of petroleum energy, oil pollution becomes the most common and serious pollution in marine pollution. In a polluted water body, oil floating on the water surface forms a film, and the dissolution of oxygen in the atmosphere is influenced, so that the survival of fish and the self-cleaning effect of the water body are influenced. Meanwhile, if the greasy dirt lands on the shore, other organisms and land animals can be damaged. Such spilled oil can also pose a threat to human health through inhalation, skin and eyes. With the development of society, researchers are paying more attention to the influence of petroleum pollution on various aspects of an ecological system, and develop various measures against petroleum pollution.
The current treatment option to reduce or remove most of the dissolved oil is chemical precipitation. The common problem is that the reaction time is slow, and the dissolution of high residual metals at near neutral ph during the treatment requires the addition of polyelectrolytes or other chemicals during the coagulation and flocculation steps, as well as the reliance on many other chemicals as coagulants to further promote rapid settling. Aiming at water pollution, the adsorption method can be adopted to try to solve, and the common adsorption materials at present are active carbon, zeolite, bentonite and some industrial and agricultural wastes, however, the materials are not suitable for the construction field, but have porous properties. From this point of view, the pore structure of the oil-absorbing composite cementing material is changed into a porous structure by adding the mineral admixture and the external admixture, so that the adsorption performance of the oil-absorbing composite cementing material on oil pollution is improved.
The invention patent application document CN110721665A discloses a method for preparing a magnetic adsorption material by using mussel shells, wherein mussel powder is added into a salt solution containing manganese ions, iron ions and zinc ions for adsorption impregnation, then the mussel powder is added into a deposition solution containing carbonate or bicarbonate for codeposition, and finally the calcination treatment is carried out to enable a metal compound material layer to grow on the surface of the mussel powder to form the magnetic adsorption material, so that the oil removal and water purification are realized. However, the raw materials and the preparation process of the material are complex, and the material can not be used as a cementing material to bond aggregate, can only be used as a particle adsorbent, and is not suitable for the field of building materials. The invention patent application document CN115043632A discloses a sulfate activated fly ash cementing material and a preparation method thereof, wherein fly ash is mixed with silicate cement, sodium sulfate is added for stirring, and the fly ash cementing material is obtained, and the early strength of the cementing material is accelerated by activating the fly ash, but along with the acceleration of the hydration speed, enough pores cannot be generated in the cementing material, and the cementing material does not have the adsorption performance on greasy dirt.
Under the current situation, if the oil-absorbing composite cementing material can be developed, the oversized mineral admixture is used for replacing cement, the pore-forming adsorption performance of the cement-based material is fully exerted, the polarity is regulated and controlled by combining the modified material, the cement-based cementing material with excellent oil-absorbing performance is designed, and the basic strength of the cement stone after the cement-based cementing material is solidified is ensured. The application range of the oil stain adsorption material is greatly expanded, so that the oil absorption composite cementing material becomes a novel ecological environment functional material in the treatment of pollutants such as petroleum and the like, and the serious environmental protection problem is solved.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of an oil-absorbing composite cementing material, and a water surface oil-absorbing floating block is obtained according to the formed cementing material, a large number of capillary holes are formed in the cementing material after a large number of fly ash, slag and modified scallop powder are added, so that a space for capturing oil stains is provided, and meanwhile, the oil-absorbing performance is further improved by adding high molecular weight polyethylene glycol, polypropylene fiber, siloxane and other nonpolar substances to modify the internal pores of the cementing material.
In order to achieve the above purpose, the invention discloses the following technical scheme:
in a first aspect of the present invention, there is provided a method of preparing an oil absorbing composite cementitious material, wherein the cementitious material comprises the following components: cement, fly ash, slag, shell powder, polyethylene glycol, silane impregnant and fiber, wherein the mass percentage of the solid components is 5-20% of cement, 50-70% of fly ash, 10-20% of slag, 2-20% of shell powder, 0.2-5% of polyethylene glycol, 0.07-0.70% of silane impregnant and 0.1-0.3% of fiber, and the polyethylene glycol is 8000-20000; the preparation method comprises the following preparation steps:
S1, modifying shell powder:
s11, removing organic impurities from shells, and crushing the shells to prepare shell powder;
s12, immersing shell powder in a citric acid solution, soaking for 40-60 min by utilizing ultrasonic waves, and cleaning in water until the shell powder is neutral;
s13, soaking in NaOH for three times and soaking in hydrochloric acid, sequentially soaking in NaOH of 18-25% for 15-30 min, washing in water to be neutral, soaking in NaOH of 5-12% for 30-40 h, and washing in water to be neutral; soaking in hydrochloric acid for 2-4 h, and washing in water to neutrality; soaking 40-60% NaOH for the third time for 20-30 h;
s14, treating the shell powder by microwaves for 30-60 min;
s2, modifying the fiber by mixing and stirring with a silane impregnant, and drying at room temperature for 46-48 hours;
s3, mixing and stirring to obtain a cementing material, which specifically comprises the following substeps:
s31, putting cement, fly ash, slag, modified shell powder and modified fiber into a paste mixer, and mixing for 3-5 min at a rotating speed of 135-145 r/min to obtain a mixture;
s32, stirring polyethylene glycol, a silane impregnant and water by using a magnetic stirrer until the polyethylene glycol is dissolved in the water to obtain a mixed solution;
s33, adding the mixed solution into the mixture, and stirring at the rotating speed of 135-145 r/min for 1-2 min to obtain the cementing material.
It is preferable that the modifications applied in step S2 and step S3 are specifically:
in the modification process, the modified shell powder comprises a first modification source, a second modification source, a third modification source and a fourth modification source, the pores of the shell powder are uniformly distributed, and after the shell powder is modified, the shell contains chitin (C) 8 H 13 O 5 N) n Deacetylation to chitosan (C) 6 H 11 NO 4 ) n The method comprises the steps of carrying out a first treatment on the surface of the The chitosan long-chain molecules are crosslinked with the fly ash matrix, so that the formation of a three-dimensional reticular pore structure is promoted; the most probable pore diameter of the cementing material is between 100 and 1000nm, and meanwhile, the pore is regulated by adopting intermittent grading according to the particle sizes of the fly ash and slag, the mixing amount of the fly ash is 50 to 70 percent, the pore volume of 100 to 1000nm in the cementing material accounts for more than 50 percent of the total pore volume after the cementing material is cured, and the cementing material is used as an oil absorption and storage pore canal to form a first modified source;
the silane impregnant hydrolyzes three Si-X groups connected with silicon into silicon hydroxyl groups (Si-OH) under alkaline conditions, the hydrolyzed silicon hydroxyl groups react with hydroxyl groups in the cementing material to generate condensation, silane is combined with the cementing material, alkyl groups are attached to the inside of the oil-absorbing composite cementing material after polymerization reaction to reduce the surface energy of the oil-absorbing composite cementing material, and the silane impregnant acts together with the micro-nano structure in the oil-absorbing composite cementing material to enable the surface of the oil-absorbing composite cementing material to form a carbon chain oleophylic and hydrophobic surface layer connected with the silicon hydroxyl groups to form a second modification source;
The molecular formula of the polypropylene fiber comprises nonpolar-CH 3-CH3-CH 3-long chains, the polypropylene fiber is modified by a silane impregnant, a layer of waterproof high molecular compound with a plurality of molecular thicknesses is generated on the surface of the polypropylene fiber, so that the polypropylene fiber has hydrophobic oil absorption performance, and meanwhile, the crisscross network structure among the fibers further weakens the polarity of the oil absorption composite cementing material to form a third modification source;
when the concentration of polyethylene glycol adsorbed on the surface of the cementing material particles is increased, the repulsive force between molecular chain segments adsorbed on the surfaces of the particles is increased, and the arrangement is compact, so that lipophilic groups in the polyethylene glycol molecular chain segments are extruded to the outer sides of the particles, C-S-H and-O-are prevented from contacting with water, and a lipophilic layer is formed on the surfaces of the cementing material particles, so that a fourth modification source is formed.
It may be preferable to regulate the mass ratio between the first modified source and the second modified source, the third modified source and the fourth modified source, when the ratio of the mass ratio between the first modified source and the second modified source, the third modified source and the fourth modified source is in the range of 68 to 92, that is, when the ratio of the specific surface area of the cement to the-CH 2-and-CH 3-long chain methyl groups is a preset value, the cement is obtained.
Preferably, the shell powder is one of scallop powder and mussel powder; the grain size of the shell powder is between 0.08 and 0.6mm, the first soaking concentration of NaOH is 20mol/L, and the second soaking concentration of NaOH is 6mol/L.
Preferably, the silane impregnant in step S2 is at least 1 of siloxane and isooctyltriethoxysilane; the fiber is at least 1 of polypropylene fiber and polyester fiber; the cement in the step S3 is P.II 42.5 silicate cement; the fly ash is II-grade fly ash; the slag is S95 grade fine grinding slag.
In a second aspect of the invention, there is provided a water surface oil-absorbing floating block comprising an oil-absorbing composite cementitious material prepared by the aforementioned method for preparing an oil-absorbing composite cementitious material, the water surface oil-absorbing floating block being obtained by bonding ceramic particles as pervious concrete coarse aggregate with a cementitious material,
the water surface oil-absorbing floating block comprises, by mass, 4-10% of cement, 28-38% of fly ash, 2-10% of slag, 2-10% of shell powder, 0.2-1.2% of polyethylene glycol, 0.03-0.50% of a silane impregnant, 0.05-0.09% of fibers and 45-60% of ceramsite, wherein the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000.
Further, the preparation process of the water surface oil-absorbing floating block further comprises the following steps:
s4, spraying water to wash the ceramsite for 30min, and filtering;
s5, adding the ceramsite cleaned in the step S4 into the cementing material obtained in the step S3, placing the cementing material into a concrete mixer, and stirring at a rotating speed of 135-145 r/min for 3min to obtain the oil-absorbing and water-permeable ceramsite concrete;
s6, placing the prepared haydite concrete into a mould, standing for 48 hours in an environment with the temperature of 24+/-1 ℃ and the relative humidity of 50+/-1%, removing the mould, placing the mould into a curing box with the temperature of 20+/-1 ℃ and the relative humidity of 100+/-1%, and curing to obtain floating blocks with preset age;
and S7, taking out the floating blocks which are maintained to a preset age, standing until the surfaces are dry, and brushing a silane impregnant.
Further, the ceramsite is shale ceramsite.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional cementing material, the main materials of the invention are fly ash, slag and scallop powder, and only contain a small amount of cement, which is helpful for solving various environmental pollution problems caused by solid waste stockpiling; the problems of high energy consumption and high pollution generated in the traditional cement production are reduced to a certain extent, and the requirements of energy conservation, emission reduction and green sustainable development are met.
2. According to the invention, the pores of the oil-absorbing composite cementing material are regulated and controlled by adding fly ash, modified shells and the like, and the oil-absorbing pore canal is subjected to nonpolar modification by adding modified fiber material oil-absorbing and silane impregnant and polyethylene glycol, so that the oil-absorbing pore diameter and the oil-absorbing performance of the traditional cementing material are far superior. By changing the problem that the existing granular oil absorption material is difficult to recycle by throwing on the water surface, the cementing material can adsorb oil stains by means of a water body structure or a floating block.
3. The invention adopts the silane impregnant to modify the surface of the oil-absorbing composite cementing material, so that a layer of carbon chain hydrophobic layer connected by silicon hydroxyl groups is formed on the surface of the oil-absorbing composite cementing material, thereby converting the typical hydrophilic characteristic into hydrophobic property, achieving the effect of hydrophobic and oleophylic, and improving the oil-absorbing performance of the composite cementing material. The cement-based adhesive material is formed by mixing cement, fly ash, slag and shell powder, and further enhances the oil absorption and oil storage capacity of the oil-absorbing composite adhesive material.
4. Traditional cement glue material does not have greasy dirt adsorption design, so that even for functional concrete with higher adsorption requirement, the cement glue material does not have the greasy dirt adsorption function. The oil absorption glue material effectively solves the problem that concrete is used as a polar material and has poor oil absorption, and can be used for filling and bonding various functional concrete.
5. The invention adopts the designed adhesive to bond the coarse aggregate of the ceramsite, so as to prepare the ceramsite permeable concrete product, namely the water surface oil stain absorbing floating block. The floating block has large quantity and good adsorptivity, can float and is favorable for recovery, secondary pollution is not caused, and the oil absorption performance and the oil storage performance of the floating block on the basis of ceramsite are further enhanced.
Drawings
FIG. 1 is a schematic flow chart of a method for preparing an oil absorbing composite gel material of the present invention;
FIG. 2 is a schematic diagram of the surface mechanism of the siloxane modified cement stone of the invention;
FIG. 3 is a schematic diagram of sensitivity analysis of various factors of the present invention to porosity at different levels;
FIG. 4 is a schematic diagram showing the sensitivity analysis of the oil absorption at different levels for each of the factors of the present invention;
FIG. 5 is a graph showing oil absorption versus the present invention.
Detailed Description
The invention provides an oil-absorbing composite cementing material with higher oil absorption than the traditional cementing material on the premise of ensuring the basic strength. According to the technical scheme, compared with the content of CaO in cement, the content of the fly ash and slag is less, more water is reserved in the oil-absorbing composite cementing material in the hydration process, a large amount of uneven pores remain after the water in the oil-absorbing composite cementing material is evaporated and can be used as an oil storage space, meanwhile, the shell is used as a natural material and is generally composed of a protein outer layer, a calcite middle layer and a calcium carbonate crystal inner layer, the structure is relatively loose, the pore diameter is relatively large, the pore distribution is wide and uniform, and the pore surface is rough, so that the oil-absorbing composite cementing material has a certain capturing capability on oil stains and also has good oil retention property. The pore of the oil-absorbing composite cementing material is regulated and controlled by using the components of materials such as fly ash, modified scallop powder, slag and the like, so that the porous composite cementing material is formed complementarily. The relation between the mixing amount of the main fly ash of the cementing material and the pore structure is as follows:
ROI＝m+aexp[(x-b)/t]
Wherein x is the mass percent of the fly ash content in the cementing material, the ROI value is the ratio of pore volume of capillary pores (100-1000 nm) to the total pore volume of the sample, and a and b are fitting coefficients.
The pore distribution of the shell powder is wide and uniform, the shell powder with the grain diameter of 0.08-0.6 mm is calcined at high temperature through a specific modification process to remove carbonate and protein, and the following chemical reaction occurs:
2C 6 H 8 O 7 +3CaCO 3 ＝(C 6 H 5 O 7 )2Ca 3 +3CO 2 ↑+3H 2 O
shell contains chitin (C) 8 H 13 O 5 N) n Deacetylation can generate chitosan (C) through a modification process under a strong alkali environment 6 H 11 NO 4 ) n The following chemical reactions occur:
the chitosan long-chain molecules are crosslinked with the fly ash matrix, so that the formation of a three-dimensional reticular pore structure is promoted. The addition of a proper amount of chitosan is beneficial to the development of the cement glue material strength, and the chitosan long-chain molecules and the fly ash matrix are crosslinked to form a three-dimensional network structure together, so that the combination degree of the geopolymer structure is improved, and the toughness is improved; on the other hand, chitosan can also form a more compact geopolymer structure, thereby improving strength. When the mixing amount of the chitosan is continuously increased, the flexural strength and the compressive strength of the fly ash simultaneously tend to be reduced, because the excessive chitosan and the fly ash have the problem of two-phase incompatibility. In addition, when the chitosan content is too high, the chitosan particles can wrap the fly ash particles, so that further dissolution and polycondensation of the particles are hindered, and the flexural strength and the compressive strength are reduced. Through experimental and semi-empirical theory, the stable relation between the oil absorption pore diameter and the strength can be obtained only under the component proportion designed by the invention.
The high molecular weight polyethylene glycol is a nonionic surfactant, and the bridging oxygen atom in the polyethylene glycol is-O-hydrophilic, -CH 2 -CH 2 -oleophilic. When the concentration of polyethylene glycol adsorbed on the surface of the cementing material particles is increased, the repulsive force between the molecular chain segments adsorbed on the surfaces of the particles is increased, the arrangement tends to be compact, and lipophilic groups in the polyethylene glycol molecular chain segments are extruded to the outer sides of the particles, so that the wettability of the surfaces of the cementing material particles is changed. The static charges can be locally generated on the cement particles, so that the polar seepage medium is polarized, the dipole moment of water molecules passing through the pores is increased, and the seepage resistance of water is increased. Meanwhile, local static charges have little influence on nonpolar oil, and oil molecules are bound on high polymers and high polymer molecular chains adsorbed on the surfaces of pores, so that the surfaces of the cementing material particles are oil-wet. Through continuous attempts, the oil absorption increase only appears in a limited range when the polyethylene glycol addition amount is changed, and the change trend is consistent with the expected change. The molecular formula of the polypropylene fiber is mainly composed of nonpolar-CH 3 -CH 3 -CH 3 The long chain composition, the network structure formed by crisscross of the long chain composition enables the long chain composition to have a very large specific surface area, and meanwhile, the polarity of the cementing material is further weakened by the crisscross network structure among fibers, so that the oil absorption performance of the cementing material is enhanced. When polyethylene glycol and polypropylene fibers are doped, C-S-H and nonpolar-CH 2-CH2-, -CH are reasonably regulated 3 -CH 3 -CH 3 The ratio of the long chains reaches the joint of permeation, storage and adsorption. Under the combined action of the two, the adsorption capacity of the oil stain is larger than that of one material used independently, the two materials are nonpolar substances, the oil stain is also nonpolar substances, and the oil stain is adsorbed according to the similar principle of intermiscibility: the interaction of solute particles and solvent particles in the solution causes dissolution and promotes the adsorption of greasy dirt.
On the basis, siloxane or isooctyltriethoxysilane is adopted to modify the surface of the solidified cementing material, three Si-X groups connected with silicon can be hydrolyzed into silicon hydroxyl groups (Si-OH) under alkaline conditions, and two condensation reactions can occur on the silicon hydroxyl groups: the silicon hydroxyl groups are mutually dehydrated and condensed into oligosiloxane containing silicon hydroxyl groups, and the silicon hydroxyl groups and-OH on the surface of the cementing material matrix undergo condensation reaction to form hydrogen bonds, as shown in figure 2.
The modification reaction equation of the isooctyltriethoxysilane for regulating and controlling the non-polarity of the pore surface of the adhesive material is as follows: 2CH 3 Si(OH) 2 ONa+CO 2 +H 2 O→2CH 3 Si(OH) 3 +Na 2 CO 3n Ch 3 Si(OH) 3 →[CH 3 SiO 3/2 ] n +3/2H 2 O
The hydrolyzed silicon hydroxyl groups are condensed after reacting with hydroxyl groups in the cementing material and silane is combined with the cementing material. The alkyl is attached to the inside of the solidified cementing material after the polymerization reaction, so that the surface energy of the cementing material is reduced, and the alkyl acts together with the micro-nano structure in the cementing material, so that a carbon chain hydrophobic layer connected with silicon hydroxyl is formed on the surface of the solidified cementing material, the surface layer of the solidified cementing material is converted from typical hydrophilic property to hydrophobic property, and the effects of hydrophobicity and oleophylic property are achieved. By regulating the pore size of the cementing material and the dosage of the nonpolar material, the oil absorption performance is greatly increased when the ratio of the pore size of the cementing material to the dosage of the nonpolar material is 68-92, namely when the ratio of the specific surface area of the cementing material to the-CH 2-CH 2-and-CH 3-CH 3-long chain methyl groups is a preset value. Can effectively replace traditional cementing materials in the fields of slope protection and the like, realize the cooperative utilization of multiple solid wastes, improve the oil absorption performance of the cement-based composite material and reduce the environmental pollution.
As shown in fig. 1, the invention provides a preparation method of an oil-absorbing composite cementing material, wherein the cementing material comprises the following components: cement, fly ash, slag, shell powder, polyethylene glycol, silane impregnant and fiber, wherein the mass percentage of the solid components is 5-20% of cement, 50-70% of fly ash, 10-20% of slag, 2-20% of shell powder, 0.2-5% of polyethylene glycol, 0.07-0.70% of silane impregnant and 0.1-0.3% of fiber, and the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000; the preparation method comprises the following preparation steps:
s1, removing organic impurities from shells, crushing the shells to prepare shell powder, immersing the shell powder into citric acid solution, treating the shell powder by utilizing ultrasonic waves for 40-60 min, cleaning the shell powder in water to be neutral, sequentially immersing the shell powder in 18-25% NaOH for 15-30 min for the first time, cleaning the shell powder in water to be neutral, immersing the shell powder in 5-12% NaOH for the second time for 30-40 h, and cleaning the shell powder in water to be neutral; soaking in hydrochloric acid for 2-4 h, and washing in water to neutrality; soaking 40-60% NaOH for the third time for 20-30 h, and treating the shell powder for 30-60 min by adopting microwave power at 460-480W;
s2, modifying the fiber by mixing and stirring with a silane impregnant, and drying at room temperature for 46-48 hours;
S3, mixing and stirring to obtain a cementing material, which specifically comprises the following substeps:
s31, putting cement, fly ash, slag, modified shell powder and modified fiber into a paste mixer, and mixing for 3-5 min at a rotating speed of 135-145 r/min to obtain a mixture;
s32, stirring polyethylene glycol, a silane impregnant and water by using a magnetic stirrer until the polyethylene glycol is dissolved in the water to obtain a mixed solution;
s33, adding the mixed solution into the mixture, and stirring at the rotating speed of 135-145 r/min for 1-2 min to obtain the cementing material.
With respect to the first aspect of the present invention, the following examples are provided.
Example 1:
the cementing material comprises the following components: cement, fly ash, slag, shell powder, polyethylene glycol, silane impregnant and fiber, wherein the mass percentage of the solid components is 5-20% of cement, 50-70% of fly ash, 10-20% of slag, 2-20% of shell powder, 0.2-5% of polyethylene glycol, 0.07-0.70% of silane impregnant and 0.1-0.3% of fiber, the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000, and the shell powder is one of scallop powder or mussel powder, and the preparation method comprises the following steps:
s1, removing organic impurities from scallops, crushing the scallops to prepare scallop powder, immersing the scallop powder in citric acid solution, performing ultrasonic treatment for 40min, cleaning the scallop powder in water to be neutral, sequentially immersing the scallop powder in 20% NaOH for 20min for the first time, immersing the scallop powder in 10% NaOH for 30h for the second time, and cleaning the scallop powder to be neutral; soaking in hydrochloric acid for 2h, and cleaning to neutrality; soaking in 50% NaOH for 20 hr, and treating scallop powder with microwave for 30min;
S2, modifying the fiber by means of mixing and stirring by using a silane impregnant, and drying at room temperature for 48 hours;
s3, adding 80g of cement, 280g of fly ash, 40g of slag and 40g of scallop powder into a stirrer, rapidly stirring for 60S, then adding 0.8g of fiber for modification, and placing into the stirrer to stir for 3min at a rotating speed of 135-145 r/min to obtain a mixture; stirring 4g of polyethylene glycol with molecular weight of 20000, 3g of silane impregnant 200g with water until the polyethylene glycol is completely dissolved in the water; adding water containing polyethylene glycol into the uniformly stirred mixture, and putting the mixture into a stirrer to stir at a rotating speed of 135-145 r/min for 2min to obtain a cementing material;
s4, in order to test the oil absorption performance of the cementing material, the prepared cementing material is put into a die in two layers, and is leveled by a seeder when the first layer is put into the die, and then is tapped for 60 times; loading the second layer, leveling with a seeder, compacting for 60 times, and then leveling with a metal ruler; standing for 48 hours at the temperature of 24+/-1 ℃ and the relative humidity of 50+/-1%, removing the mould, putting into a curing box at the temperature of 20+/-1 ℃ and the relative humidity of 100+/-1%, and curing to obtain the oil-absorbing composite cementing material with the preset age;
s5, taking out the oil-absorbing composite cementing material which is maintained to a preset age, standing until the surface is dry, and brushing 6g of silane impregnant to obtain a sample 1;
S6, placing the prepared sample 1 into a drying oven with the temperature of 65+/-1 ℃ to obtain constant weight, taking out the sample 1, cooling the sample 1, measuring the initial mass, placing the sample in a water-oil environment for 48 hours, taking out the sample 1, placing the sample 1 into the drying oven with the temperature of 65+/-1 ℃ again to obtain the mass after drying the sample to the constant weight to measure the oil absorption, and calculating the maximum oil absorption of the sample 1 in the water-oil environment; the mixing ratio molding 6-die test piece is used for testing the strength of 7 days, 28 days and 60 days respectively, and absorbing oil and energy in a water-oil environment.
Comparative example 1:
the cement with the mass percentage of the cementing material calculated by the solid component is 100 percent, and comprises the following concrete steps:
s1, adding 400g of cement and 200g of water into a stirring pot and stirring to obtain a cementing material, wherein the specific stirring mode is the same as that of the embodiment 1;
s2, filling, curing and surface treatment of the oil-absorbing composite cementing material are the same as those of the embodiment 1, so as to obtain a comparison sample 1;
s3, testing the strength and oil absorption performance of the oil absorption composite cementing material is consistent with those of the embodiment 1.
Example 2:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference from example 1 is that the amounts of the materials used in step S3 are 80g of cement, 240g of fly ash, 80g of slag, 8g of scallop powder, 2g of polyethylene glycol with molecular weight 8000, 2.6g of silane impregnant, 160g of water, and 0.8g of fiber.
Comparative example 2:
the cementing material components are consistent with comparative example 1, and the specific steps are as follows:
the difference from comparative example 1 is that 160g of water was added in step S1.
Example 3:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference with the embodiment 1 is that in the step S1, mussels are crushed into mussel powder after removing organic impurities, immersed in citric acid solution and treated by ultrasonic for 60min, washed to be neutral in water, soaked for 20min by 20% NaOH for the first time, soaked for 40h by 10% NaOH for the second time, and washed to be neutral; soaking in hydrochloric acid for 4 hours, and cleaning to neutrality; soaking in 50% NaOH for 30 hr, and treating mussel powder with microwave for 60min; the dosage of each material in the S3 step is 60g of cement, 260g of fly ash, 80g of slag, 40g of mussel powder, 0.8g of polyethylene glycol with molecular weight 20000, 1.8g of silane impregnant, 224g of water and 2g of fiber.
Comparative example 3:
the cementing material components are consistent with comparative example 1, and the specific steps are as follows:
the difference from comparative example 1 is that 224g of water was added in step S1.
Example 4:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference from example 1 is that the amount of each material used in the S3 step is 80g cement, 280g fly ash, 40g slag, 20g scallop powder, 4g polyethylene glycol with molecular weight 10000, 2.8g silane impregnant, 224g water, 0.4g fiber.
Example 5:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference with the embodiment 1 is that in the step S1, mussels are crushed into mussel powder after removing organic impurities, immersed in citric acid solution and treated by ultrasonic for 50min, washed to be neutral in water, soaked for 20min by 25% NaOH for the first time, soaked for 30h by 5% NaOH for the second time, and washed to be neutral; soaking in hydrochloric acid for 4 hours, and cleaning to neutrality; soaking in 60% NaOH for 30 hr, and treating mussel powder with microwave for 45min; the dosage of each material in the S3 step is 80g of cement, 280g of fly ash, 40g of slag, 20g of mussel powder, 2g of polyethylene glycol with molecular weight 10000, 3g of silane impregnant, 224g of water and 0.8g of fiber.
Example 6:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference with the embodiment 1 is that in the step S1, scallop is crushed into scallop powder after removing organic impurities, immersed in citric acid solution, treated by ultrasonic for 60min, washed to be neutral in water, soaked for 30min by 25% NaOH for the first time, soaked for 40h by 12% NaOH for the second time, and washed to be neutral; soaking in hydrochloric acid for 4 hours, and cleaning to neutrality; soaking in 60% NaOH for 30 hr, and treating scallop powder with microwave for 60min; and S3, the scallop powder is 20g, and 224g of water is added.
Example 7:
the cement composition was identical to that of example 1, the specific procedure being as follows:
the difference from example 2 is that the scallop powder in the S3 step is 40g, the fiber is 1.2g, the polyethylene glycol is 2g, and the water is 200g.
In a second aspect of the invention, there is provided the use of the cementing material prepared as described above to form a water surface oil-absorbing floating block, wherein the cementing material is bonded with ceramsite as a pervious concrete coarse aggregate, the cementing material comprises, by mass, 5-10% of cement, 30-50% of fly ash, 2-5% of slag, 2-5% of shell powder, 0.2-3% of polyethylene glycol, 0.03-0.50% of silane impregnant, 0.05-0.12% of fiber and 45-60% of ceramsite, wherein the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000, and the shell powder is one of scallop powder or mussel powder.
The invention discloses a floating block for absorbing greasy dirt on water surface, which comprises the following preparation steps:
s1, removing organic impurities from shells, crushing the shells to prepare shell powder, immersing the shell powder into citric acid solution, treating the shell powder by utilizing ultrasonic waves for 40-60 min, cleaning the shell powder in water to be neutral, sequentially immersing the shell powder in 18-25% NaOH for 15-30 min for the first time, cleaning the shell powder in water to be neutral, immersing the shell powder in 5-12% NaOH for the second time for 30-40 h, and cleaning the shell powder in water to be neutral; soaking in hydrochloric acid for 2-4 h, and washing in water to neutrality; soaking 40-60% NaOH for the third time for 20-30 hours, and treating the shell powder for 30-60 minutes by adopting microwaves;
S2, modifying the fiber by means of mixing and stirring by using a silane impregnant, and drying at room temperature for 46-48 h;
s3, mixing cement, fly ash, shell powder and slag, then adding fiber for modification, and stirring at a rotating speed of 135-145 r/min for 3min to obtain a mixture; stirring polyethylene glycol, silane impregnant and water until the polyethylene glycol is dissolved in the water; adding water containing polyethylene glycol into the uniformly stirred mixture, and putting the mixture into a stirrer to stir at a rotating speed of 135-145 r/min for 1-2 min to obtain a cementing material;
s4, spraying water to wash the ceramsite for 30min, and filtering;
s5, adding the ceramsite cleaned in the step S4 into the cementing material obtained in the step S3, placing the cementing material into a concrete mixer, and stirring at a rotating speed of 135-145 r/min for 3min to obtain the oil-absorbing and water-permeable ceramsite concrete;
s6, placing the prepared haydite concrete into a mould, standing for 48 hours in an environment with the temperature of 24+/-1 ℃ and the relative humidity of 50+/-1%, removing the mould, placing the mould into a curing box with the temperature of 20+/-1 ℃ and the relative humidity of 100+/-1%, and curing to obtain floating blocks with preset age;
and S7, taking out the floating blocks which are maintained to a preset age, standing until the surfaces are dry, and brushing a silane impregnant.
For the second aspect of the present invention, the following embodiments are provided.
Example 8:
the floating block for sucking greasy dirt on water surface comprises 5-10% of cement, 30-50% of fly ash, 2-5% of slag, 2-5% of shell powder, 0.2-3% of polyethylene glycol, 0.03-0.50% of silane impregnant, 0.05-0.12% of fiber and 45-60% of ceramsite, wherein the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000; the shell powder is one of scallop powder and mussel powder. The method comprises the following specific steps:
s1, a shell powder treatment step is the same as that of the embodiment 1;
s2, the fiber treatment step is the same as that of the embodiment 1;
s3, uniformly mixing 20g of cement, 160g of fly ash, 20g of scallop powder and 20g of slag, then adding 1.2g of fiber for modification, and stirring at a rotating speed of 135-145 r/min for 3min to obtain a mixture; stirring 2g of polyethylene glycol with molecular weight 10000, 1.3g of silane impregnant and 100g of water until the polyethylene glycol is completely dissolved in the water; adding water containing polyethylene glycol into the uniformly stirred mixture, and putting the mixture into a stirrer to stir at a rotating speed of 135-145 r/min for 2min to obtain a cementing material;
s4, spraying water to wash the ceramsite for 30min, and drying the ceramsite after water filtering;
S5, adding 200g of the ceramsite cleaned in the step S4 into the cementing material obtained in the step S3, placing the cementing material into a concrete mixer, and stirring at a rotating speed of 135-145 r/min for 3min to obtain the oil-absorbing and water-permeable ceramsite concrete;
s6, placing the prepared haydite concrete into a mould, standing for 48 hours in an environment with the temperature of 24+/-1 ℃ and the relative humidity of 50+/-1%, removing the mould, placing the mould into a curing box with the temperature of 20+/-1 ℃ and the relative humidity of 100+/-1%, and curing to obtain floating blocks with preset age;
s7, taking out the floating blocks which are maintained to a preset age, standing until the surfaces are dry, and brushing 7.8g of silane impregnant to obtain a sample 8;
s8, testing the oil stain adsorption performance is consistent with example 1.
Comparative example 4:
the floating block for sucking greasy dirt on water surface consists of cement 40-55 wt% and haydite 45-60 wt%.
The method comprises the following specific steps:
s1, stirring 160g of cement and 200g of water for 3min at a rotating speed of 135-145 r/min to obtain a cementing material;
s2, ceramsite treatment is the same as in example 8;
s3, adding 240g of the ceramsite cleaned in the step S2 into the cementing material obtained in the step S1, placing the cementing material into a concrete mixer, and stirring at a rotating speed of 135-145 r/min for 3min to obtain oil-absorbing and water-permeable ceramsite concrete;
S4, curing method is the same as in the embodiment 8;
s5, obtaining a comparative sample 4 by adopting the same surface treatment method as in the example 8;
s6, testing the oil stain adsorption performance is consistent with the embodiment 1.
Example 9:
the components of the floating block for sucking oil stains on the water surface are consistent with those of the embodiment 8, and the specific steps are as follows:
the difference from example 8 is that the amount of each material used in the S3 step is 40g cement, 120g fly ash, 10g scallop powder, 20g slag, 0.8g polyethylene glycol with molecular weight 20000, 1.2g silane impregnant, 100g water, 0.4g fiber; and S5, the material consumption in the step is 240g of ceramsite.
Comparative example 5:
the components of the floating block for sucking oil stains on the water surface are the same as those of the comparative example 4, and the specific steps are as follows:
the difference from comparative example 4 is that the amount of each material used in the S1 step is 200g of cement, 80g of water; and S3, the material consumption in the step is 200g of ceramsite.
Example 10:
the components of the floating block for sucking oil stains on the water surface are consistent with those of the embodiment 8, and the specific steps are as follows:
the difference from example 8 is that the amount of each material used in the S3 step is 30g cement, 130g fly ash, 5g scallop powder, 25g slag, 1g polyethylene glycol with molecular weight 8000, 0.9g silane impregnant, 100g water, 0.4g fiber; and S5, the material consumption in the step is 240g of ceramsite.
Comparative example 6:
the components of the floating block for sucking oil stains on the water surface are the same as those of the comparative example 4, and the specific steps are as follows:
the difference from comparative example 4 is that the amount of each material used in the S1 step is 200g of cement, 100g of water; and S3, the material consumption in the step is 200g of ceramsite.
Table 1 oil absorbing composite gel sample strength characteristics
| Test item | 7 day strength (MPa) | 28 day strength (MPa) | 60-day strength (MPa) |
| Example 1 | 10.5 | 19.8 | 23.7 |
| Example 2 | 11.4 | 19.1 | 23.3 |
| Example 3 | 10.3 | 20.2 | 24.8 |
| Example 4 | 9.8 | 16.0 | 20.3 |
| Example 5 | 11.8 | 18.4 | 21.7 |
| Example 6 | 10.3 | 19.6 | 23.1 |
| Example 7 | 11.4 | 18.5 | 22.3 |
| Comparative example 1 | 19.9 | 29.7 | 31.6 |
| Comparative example 2 | 18.2 | 31.5 | 33.9 |
| Comparative example 3 | 18.4 | 29.3 | 31.1 |
Table 2 oil absorption characteristics of oil absorbing composite gel samples
TABLE 3 oil absorption characteristics of oil absorption float block samples
As shown in Table 1, although the early compressive strength of the sample is smaller, the sample has the characteristic of secondary hydration like fly ash and slag, and the strength of the sample still tends to increase in 28 days to 60 days, so that the strength requirement of the non-structural cementing material is met.
As shown in tables 2 and 3, the unit oil absorption of the final sample was 85kg/m 3 The above, the overall performance difference was small, but the unit oil absorption of sample 1 was relatively high. The unit oil absorption of the comparative samples was 20kg/m 3 About, and the unit oil absorption of each age was lower than that of the same water-gel ratio samples. The calculation shows that the oil absorption per unit volume of the shell cement composite cementing material and the oil absorption floating block is more than 4 times that of the control group, and the technical effect is obvious as shown in figure 5.
The cementing material can realize the high oil absorption performance of the cement stone under the condition of ensuring the strength by the pore structure regulation and modification and the method for regulating and modifying the polarity of the cementing material by the silane impregnant, the fiber and the polyethylene glycol in a specific proportion.
The method comprises the following steps: the oil absorption composite cementing material comprises a first modification source, a second modification source, a third modification source and a fourth modification source in the modification process.
The first modification source is the combined pore-forming modification of multiple mineral admixtures. The pore is regulated according to the gap gradation of the particle size of the mineral admixture, the mixing amount of the fly ash is 50-70%, and the pore volume of 100-1000 nm after the curing of the glue material can occupy more than 50% of the total pore volume, thus being used as an optimal oil storage hole. The pore distribution of the shell powder is wide and uniform, and the most probable pore diameter of the shell powder is between 100 and 1000nm after the shell powder with the particle diameter of 0.08 to 0.6mm is calcined at high temperature by a specific modification process, so that the shell powder has oil absorption holes. At the same time, the shell contains chitin (C) 8 H 13 O 5 N) n Under the environment of strong alkali, chitosan (C) can be generated by deacetylation through the modification process 6 H 11 NO 4 ) n . The chitosan long-chain molecules and the fly ash matrix are crosslinked to form a three-dimensional network structure together, so that the toughness of the oil-absorbing composite cementing material is improved, and the strength is improved. As shown in FIG. 3, A1-A3 in the influence factors of the abscissa are fly ash with the solid content of 50-70%; B1-B3 are slag with the solid content of 10-20%; C1-C3 is shell powder with solid content of 2-20%.
The second modification source is silane impregnant modification, and the oil-absorbing composite cementing material is modified to nonpolar regulation. The silane impregnant can hydrolyze three Si-R groups connected with silicon into silicon hydroxyl groups (Si-OH) under alkaline condition, the hydrolyzed silicon hydroxyl groups are condensed and combined with silane after (-OH) reaction in the oil-absorbing composite cementing material, and the silane impregnant is combined with the internal micro-nano structure of the oil-absorbing composite cementing material to form a layer of carbon chain oleophylic and hydrophobic surface layer connected with silicon hydroxyl groups on the pore surface of the cementing material, and the modification of the silane impregnant on the cementing material promotes the internal (-CH) of the cementing material 3 、-CH 2 Having hydrophobic) functional groups are increased and (-OH has hydrophilic) functional groups are decreased; at the same time, alkyl is attached to the cementing material hole after polymerizationThe surface energy of the cementing material is reduced in the gap, so that the surface energy of the cementing material is lower than the surface energy of water and higher than the surface energy of oil, and the adsorption of greasy dirt is promoted; and the silane impregnant is dissolved in oily substances, belongs to polar substances, and promotes the adsorption of greasy dirt according to the similar intermiscibility theory.
The third modification source is fiber modification, which belongs to modification by adding nonpolar materials. The molecular formula of the polypropylene fiber comprises nonpolar-CH 3 -CH 3 -CH 3 Long chains, which are themselves oleophilic, the silane impregnant and the polypropylene fiber have affinity for each other, and the polypropylene fiber is first modified by the silane impregnant to have hydrophobic oil absorption properties; wherein, the silane impregnant generates a layer of waterproof high molecular compound with a few molecules on the surface of the polypropylene fiber, which plays a role of hydrophobicity. The crisscross network structure among the hydrophobic and oleophilic fibers has the property of promoting the adsorption of greasy dirt, and forms a third modification source.
The fourth modification source is polyethylene glycol modification, which belongs to the modification of the oil absorption cementing material from polarity to nonpolar pore wall lipophilicity. Polyethylene glycol is adsorbed on the inner wall of the pore of the oil-absorbing cementing material or is emulsified with water occupying the edges, corners and dead areas in the pore, so that the property of the inner wall of the pore is changed. Oxygen atom-O-hydrophilic, -CH in high molecular weight polyethylene glycol 2 -CH 2 -lipophilicity, when the concentration of polyethylene glycol adsorbed on the surface of the particles of the binder increases, the repulsive force between the molecular segments adsorbed on the surface of the particles increases, the alignment tends to be tight, bringing about-CH 2 -CH 2 -the lipophilic group is pushed towards the outside of the particles, preventing C-S-H and-O-from contacting with water, thereby forming a lipophilic layer on the surface of the cement particles, constituting a fourth source of modification.
By regulating and controlling the mass ratio among the first modified source, the second modified source, the third modified source and the fourth modified source, the oil absorption performance of the oil absorption cementing material is more than 4 times that of the common cementing material. When the ratio of the pore structure controlling modification (first modifying source) to the polarity controlling modification (second to fourth type of modifying source) is proper, for example, when the ratio of the mass ratio between the first modifying source and the second modifying source, the third modifying source and the fourth modifying source is in the range of 68 to 92 In particular when the ratio is in the range of 80-90, the specific surface area of the oil absorption pore diameter is compared with-CH 2 -CH 2 -and-CH 3 -CH 3 -CH 3 The proportion of the long-chain methyl is in a proper range, so that the C-S-H and the lipophilic group can be effectively blocked from contacting with water, and the excessive oil absorption space occupied by water molecules is avoided while an oil transportation channel is provided. In FIG. 4, D1-D3 is polyethylene glycol with a solid content of 0.2-5% in the influence factors of the abscissa; E1-E3 is fiber with solid content of 0.1-0.2%; F1-F3 is siloxane with solid content of 0.07-0.70%.
In summary, the invention uses solid wastes such as fly ash, slag, shell powder and the like to replace the traditional cement, and simultaneously adopts nonpolar substances such as high molecular weight polyethylene glycol, fiber, siloxane and the like to modify the oil-absorbing cementing material, thus improving the oil-absorbing performance of the cementing material, and the floating block for absorbing oil stains on the water surface prepared by the shell cement composite cementing material has good floatability on the sea surface, can be recycled, and does not cause secondary pollution.
The technical features disclosed above are not limited to the combination with other features disclosed, and other combinations of the technical features can be performed by those skilled in the art according to the purpose of the invention to achieve the purpose of the invention, and various modifications made by those skilled in the art to the technical solution of the invention should fall within the scope of protection defined by the claims of the invention without departing from the design spirit of the invention.
Claims (8)
1. The preparation method of the oil-absorbing composite cementing material is characterized in that the cementing material comprises the following components: cement, fly ash, slag, shell powder, polyethylene glycol, silane impregnant and fiber, wherein the mass percentage of the solid components is 5-20% of cement, 50-70% of fly ash, 10-20% of slag, 2-20% of shell powder, 0.2-5% of polyethylene glycol, 0.07-0.70% of silane impregnant and 0.1-0.3% of fiber, and the polyethylene glycol is 8000-20000; the preparation method comprises the following preparation steps:
s1, modifying shell powder:
s11, removing organic impurities from shells, and crushing the shells to prepare shell powder;
s12, immersing shell powder in a citric acid solution, soaking for 40-60 min by utilizing ultrasonic waves, and cleaning in water until the shell powder is neutral;
s13, soaking in NaOH for three times and soaking in hydrochloric acid, sequentially soaking in NaOH of 18-25% for 15-30 min, washing in water to be neutral, soaking in NaOH of 5-12% for 30-40 h, and washing in water to be neutral; soaking in hydrochloric acid for 2-4 h, and washing in water to neutrality; soaking 40-60% NaOH for the third time for 20-30 h;
s14, treating the shell powder by microwaves for 30-60 min;
s2, modifying the fiber by mixing and stirring with a silane impregnant, and drying at room temperature for 46-48 hours;
S3, mixing and stirring to obtain a cementing material, which specifically comprises the following substeps:
s31, putting cement, fly ash, slag, modified shell powder and modified fiber into a paste mixer, and mixing for 3-5 min at a rotating speed of 135-145 r/min to obtain a mixture;
s32, stirring polyethylene glycol, a silane impregnant and water by using a magnetic stirrer until the polyethylene glycol is dissolved in the water to obtain a mixed solution;
s33, adding the mixed solution into the mixture, and stirring at the rotating speed of 135-145 r/min for 1-2 min to obtain the cementing material.
2. The method for preparing an oil absorbing composite gel material according to claim 1, wherein the modification applied in step S2 and step S3 is specifically:
in the modification process, the modified shell powder comprises a first modification source, a second modification source, a third modification source and a fourth modification source, the pores of the shell powder are uniformly distributed, and after the shell powder is modified, the shell contains chitin (C) 8 H 13 O 5 N) n Deacetylation to chitosan (C) 6 H 11 NO 4 ) n The method comprises the steps of carrying out a first treatment on the surface of the The chitosan long-chain molecules are crosslinked with the fly ash matrix, so that the formation of a three-dimensional reticular pore structure is promoted; the most probable pore diameter of the cementing material is between 100 and 1000nm, and simultaneouslyAccording to the particle size of the fly ash and slag, the gap gradation is adopted to adjust the pore, the mixing amount of the fly ash is 50-70%, the pore volume of 100-1000 nm in the cementing material after the cementing material is cured accounts for more than 50% of the total pore volume, and the pore is used as an oil absorption and storage pore canal to form a first modified source;
The silane impregnant hydrolyzes three Si-X groups connected with silicon into silicon hydroxyl groups (Si-OH) under alkaline conditions, the hydrolyzed silicon hydroxyl groups react with hydroxyl groups in the cementing material to generate condensation, silane is combined with the cementing material, alkyl groups are attached to the inside of the oil-absorbing composite cementing material after polymerization reaction to reduce the surface energy of the oil-absorbing composite cementing material, and the silane impregnant acts together with the micro-nano structure in the oil-absorbing composite cementing material to enable the surface of the oil-absorbing composite cementing material to form a carbon chain oleophylic and hydrophobic surface layer connected with the silicon hydroxyl groups to form a second modification source;
the molecular formula of the polypropylene fiber comprises nonpolar-CH 3-CH3-CH 3-long chains, the polypropylene fiber is modified by a silane impregnant, a layer of waterproof high molecular compound with a plurality of molecular thicknesses is generated on the surface of the polypropylene fiber, so that the polypropylene fiber has hydrophobic oil absorption performance, and meanwhile, the crisscross network structure among the fibers further weakens the polarity of the oil absorption composite cementing material to form a third modification source;
when the concentration of polyethylene glycol adsorbed on the surface of the cementing material particles is increased, the repulsive force between molecular chain segments adsorbed on the surfaces of the particles is increased, and the arrangement is compact, so that lipophilic groups in the polyethylene glycol molecular chain segments are extruded to the outer sides of the particles, C-S-H and-O-are prevented from contacting with water, and a lipophilic layer is formed on the surfaces of the cementing material particles, so that a fourth modification source is formed.
3. The method for preparing an oil absorbing composite cementing material according to claim 2, wherein the mass ratio between the first modified source and the second modified source, the mass ratio between the third modified source and the mass ratio between the fourth modified source are controlled within a range of 68-92, namely, when the ratio of the specific surface area of the cementing material to-CH 2-CH 2-and-CH 3-CH 3-long chain methyl is a preset value, the cementing material is obtained.
4. The method for preparing the oil absorbing composite gel material according to claim 1, wherein the shell powder is one of scallop powder and mussel powder; the grain size of the shell powder is between 0.08 and 0.6mm, the first soaking concentration of NaOH is 20mol/L, and the second soaking concentration of NaOH is 6mol/L.
5. The method for preparing an oil absorbing composite gel material according to claim 1, wherein the silane impregnant in the step S2 is at least 1 of siloxane and isooctyltriethoxysilane; the fiber is at least 1 of polypropylene fiber and polyester fiber; the cement in the step S3 is P.II 42.5 silicate cement; the fly ash is II-grade fly ash; the slag is S95 grade fine grinding slag.
6. A water surface oil-absorbing floating block is characterized by comprising the oil-absorbing composite cementing material prepared by the preparation method of the oil-absorbing composite cementing material of claim 1, wherein the water surface oil-absorbing floating block is obtained by bonding ceramic particles serving as pervious concrete coarse aggregate by adopting the cementing material,
the water surface oil-absorbing floating block comprises, by mass, 4-10% of cement, 28-38% of fly ash, 2-10% of slag, 2-10% of shell powder, 0.2-1.2% of polyethylene glycol, 0.03-0.50% of a silane impregnant, 0.05-0.09% of fibers and 45-60% of ceramsite, wherein the polyethylene glycol is polyethylene glycol with molecular weight of 8000-20000.
7. The water surface oil-absorbing floating block according to claim 1, wherein the preparation process of the water surface oil-absorbing floating block further comprises the following steps:
s4, spraying water to wash the ceramsite for 30min, and filtering;
s5, adding the ceramsite cleaned in the step S4 into the cementing material obtained in the step S3, placing the cementing material into a concrete mixer, and stirring at a rotating speed of 135-145 r/min for 3min to obtain the oil-absorbing and water-permeable ceramsite concrete;
s6, placing the prepared haydite concrete into a mould, standing for 48 hours in an environment with the temperature of 24+/-1 ℃ and the relative humidity of 50+/-1%, removing the mould, placing the mould into a curing box with the temperature of 20+/-1 ℃ and the relative humidity of 100+/-1%, and curing to obtain floating blocks with preset age;
And S7, taking out the floating blocks which are maintained to a preset age, standing until the surfaces are dry, and brushing a silane impregnant.
8. The water surface oil-absorbing floating block of claim 6, wherein the ceramsite is shale ceramsite.
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