CN110183155A - The foam concrete preparation method utilized based on process hides chrome leather scrap and gangue - Google Patents
The foam concrete preparation method utilized based on process hides chrome leather scrap and gangue Download PDFInfo
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- CN110183155A CN110183155A CN201910427839.6A CN201910427839A CN110183155A CN 110183155 A CN110183155 A CN 110183155A CN 201910427839 A CN201910427839 A CN 201910427839A CN 110183155 A CN110183155 A CN 110183155A
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- gangue
- hydrolyzate
- chrome leather
- leather scrap
- shavings
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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
- 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
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/10—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by using foaming agents or by using mechanical means, e.g. adding preformed foam
-
- 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
-
- 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
- C04B2111/40—Porous or lightweight materials
Abstract
The present invention relates to a kind of foam concrete preparation methods utilized based on process hides chrome leather scrap and gangue, using the hydrolysis of shavings, the preparation of the modified shavings hydrolyzate of rosin acyl chlorides, compounding, the process of gangue foaming processing, to prepare foam concrete.Comprehensive advantage of the invention is the fully- depleted of shavings, gangue, without secondary pollution, reaches the resource utilization purpose of waste.
Description
Technical field
The present invention relates to the methods for preparing construction material as primary raw material using waste.In particular to chromium is contained based on process hides
The foam concrete preparation method that shavings and gangue utilize.
Background technique
China is the first process hides big country in the world, about 7,000,000,000 square feet of leather annual output, accounts for about whole world total output
1/4.The waste of tannery, especially chromed leather wastes are mainly blue skin scurf, indigo plant Pi Pibian, dyeing skin side and cover with paint, lacquer, colour wash, etc. skin
Side etc., meanwhile, the discarded major part of the cornu cutaneum that Leather Shoes Factory, leatherware factory and sofa Chang Deng leather and fur products processing enterprise generate, which belongs to, to be contained
Chromium waste.Signified chrome leather scrap of the invention is caused when referring to Lan Geyong split Bigpian into one layer or multi-ply construction
Blocky and sheet waste, and indigo plant is removed from office to leftover bits and pieces caused when being whittled into required width using shaving machine, it is mainly process hides
After factory's tanning when shaving caused by chrome shavinge (chromeshavings), the Cr containing 3.5%-4.0%2O3With more than 90%
Collagen, due to contain crome metal, be one of Leather-Industrial Pollution source.Currently, the leather leftover that pile up like a mountain, serious to restrict
The development of curriery, be tannery face and urgent need to resolve technical problem.
The conventional process mode of chrome leather scrap is for gelatin processed or albumen powder, and gelatin processed is big in the presence of wastewater flow rate is generated,
And lead to the problem of secondary waste；Albumen powder processed can also be related to leading to the problem of secondary waste.
Gangue is the solid waste discharged during coal mining process and coal washing, be one kind in coalification course with coal seam
A kind of lower, harder than the coal black and gray rock of phosphorus content of association.Including the digging gangue during tunnelling, digging
The spoil produced in top plate and bottom plate and interlayer in the process and that chooses during coal washing wash spoil.Gangue main component
It is Al2O3、SiO2, in addition also contain Fe in varying numbers2O3、CaO、 MgO、Na2O、K2O、P2O5、SO3With micro rare element
(gallium, vanadium, titanium, cobalt).
Gangue is thrown aside, and tract is occupied.In addition, the sulfide evolution or leaching in gangue can pollute greatly
Gas, farmland and water body.Hillock can also spontaneous combustion fire occurs, or in rainy season avalanche, silt river up and cause disaster.It is Chinese current
Accumulate gangue up to 1,000,000,000 tons or more, every year also by 100,000,000 tons or so of newly-increased gangue.In order to eliminate pollution, from the sixties,
Many countries start to pay attention to the processing and utilization of gangue.Such as: coal gangue subculture replaces turning sludge into fuel iron, burning boiler, and burnt lime returns
Receive coal etc..Ordinary portland cement is produced for another example.Produce special cement, production clinker-free cement etc..Production is built for another example
Material is built, with coal gangue baked brick, quality is preferable, and color is uniform.For another example gangue produce lightweight aggregate, lightweight aggregate be in order to
A kind of porous aggregate for reducing the relative density of concrete and selecting.Coal gangue wool is produced, for another example with gangue and lime
For raw material, through high temperature melt, blowing forms a kind of construction material.Chemical products are produced for another example: crystal aluminum chloride processed, with
Gangue and chemical engineering industry by-product hydrochloric acid are primary raw material, by be crushed, roast, grinding, acidleach, precipitating, condensing crystallizing and are taken off
The production technologies such as water and be made, be a kind of novel water purification agent；Waterglass processed；Ammonium sulfate is produced, the iron sulfide in gangue exists
SO2 is produced under high temperature, reoxidizes and produces SO3, meets aquatic production sulfuric acid, and the production of chemicals ammonium sulfate with ammonia.
Chinese invention patent 201710977501.9 discloses a kind of enhanced colliery wastes brick, belongs to building material technology neck
Domain.According to parts by weight, 75~85 parts of gangues are successively weighed, 4~6 parts of clays, 10~15 parts of brown iron oxides, 15~25 parts
Potassium permanganate, 5~12 parts of aluminium powders, 20~23 parts of flyash and 5~8 parts of modified glass-fibers, pulverize coal gangue, and sieving obtains
Gangue powder mixes clay, brown iron oxide, potassium permanganate, aluminium powder, flyash and modified glass-fiber in ball mill,
Mixture is obtained, after mixture and gangue powder are stirred, compression moulding in mold is added, obtains blank, blank is dry
It moves into sintering furnace, sintering, after cooling to room temperature with the furnace, discharges afterwards, maintenance obtains enhanced colliery wastes brick.Its coal prepared
Spoil brick has preferable mechanical property, while scum phenomenon is reduced.
Chinese invention patent 201810186030.4 discloses a kind of tanning waste technical field of resource utilization, provides
A method of the compound biodegradable fiber of collagen-based being prepared using shavings containing metallic, extracts collagen using process hides shavings,
Solid leather wastes pollution, especially process hides noxious waste pollution containing chromium can be reduced, is turned waste into wealth, day is efficiently used
Right animal protein resource；Meanwhile the collagen of shavings preparation and polyvinyl alcohol, chitosan, sodium carboxymethylcellulose being blended and being spun
Silk, obtains compound biodegradable fiber, solves the defect of homogenous material spinning, thermal stability, water-resistance, mechanical property etc.
It all makes moderate progress, degradability is adjustable, and disadvantage is no large-scale use.
Above-mentioned two Chinese patents as the prior art propose the hydrolysis process for treating and gangue of chrome leather scrap
Utilization method as raw material of building materials.The gangue wherein referred in 201710977501.9 be as brick, at
This is higher.Wherein 201810186030.4 be that will contain metallic shavings to be processed into biodegradable fiber, but it can only partially disappear
Chrome leather scrap is consumed, it cannot batch and extensive consumption chrome leather scrap.
Summary of the invention
The technical problem to be solved by the invention is to provide a kind of bubbles utilized based on process hides chrome leather scrap and gangue
Foam concrete preparation method prepares cement blowing agent using chrome leather scrap, and using gangue and solid-state chrome leather scrap as base
Material prepares the relatively good foam concrete of a kind of compression strength, Absolute Dry Density, water absorption rate index.
The foam concrete preparation method utilized based on process hides chrome leather scrap and gangue comprising following process: shavings
Hydrolysis, the modified shavings hydrolyzate of rosin acyl chlorides preparation, compounding, gangue foaming processing；
Detailed process is as follows:
(1), chrome leather scrap hydrolyzes: chrome leather scrap is weighed as after drying to constant weight to the weight calculation radix of this step (1),
It puts into the reaction vessel with agitating device and temperature control device, addition sodium hydroxide 11%~15%, benzamide 0.2%~
0.3%, D-sorbite 0.1%~0.2% and water 800%~1200% are stirred to react 5~7h at 70~90 DEG C of temperature, drop
Temperature arrives room temperature, by being centrifugally separating to obtain hydrolyzate A, then filters to obtain hydrolyzate B through vacuum decompression, and will hydrolyze remaining residual
Remaining solid is dried for standby；
(2), the foaming agent preparation of the modified shavings hydrolyzate of rosin acyl chlorides: being dissolved after rosin is ground with benzene, and stirring is lower to be added
Enter the acylating reagent of rosin quality 40%~50%, 2~3h of insulation reaction, stratification is overnight, and next day takes out the pine on upper layer
Fragrant solution of acid chloride；
By in the reaction vessel of the hydrolyzate B investment with agitating device and temperature control device of step (1) preparation, stirring is lower to be added
Enter the rosin solution of acid chloride of hydrolyzate B mass 35%~50%, is stirred to react 2-3h at 40~60 DEG C of reaction temperature, so
Adjusting pH with concentrated hydrochloric acid afterwards is 2, and yellow mercury oxide is obtained by filtration, is cleaned with petroleum ether, obtains the modified shavings hydrolyzate of rosin acyl chlorides
Foaming agent；
(3), it compounds: foaming agent, surfactant, lauryl alcohol and substance B that step (2) is obtained, according to mass ratio
100:(10~50): (1~3): 1~2h is mixed in (2~3), obtains compositional liquor；
Wherein, substance B the preparation method comprises the following steps: Ji Wusi is added in the reaction vessel with agitating device and temperature control device
Alcohol, the maleic anhydride of pentaerythrite quality 10%~15% and the sodium methoxide of pentaerythrite quality 3%~5%, in 55~65
1~2h is reacted at DEG C, adds the n-isopropyl acrylamide and pentaerythrite quality of pentaerythrite quality 3%~5%
5%~8% dimethylphosphite is stirred to react 1~3h at 70~80 DEG C, obtains substance B；
(4), prepared by foam concrete: gangue, cement, calcium chloride, ethylhexyl palmitate, versatic acid being shunk sweet
After mixing, the compositional liquor that step (3) obtain is added in the residual solid for the drying that grease and step (1) obtain, and continues
Stirring, obtains the foam concrete utilized based on process hides chrome leather scrap and gangue；
Wherein, gangue, cement, calcium chloride, ethylhexyl palmitate, tertiary carbonic acid glycidyl ester, step (1) obtain
Drying residual solid and the obtained compositional liquor of step (3) between mass ratio are as follows: (20~200): (595~775):
(3~8): (1~2): (2~3): (5~10): (200~300).
Preferably, step (4) specific practice:
1) gangue, is subjected to scalping, screens out the stone of larger particles, takes the remaining baking oven that is put into dry, takes in proportion
The gangue of drying, 42.5 class g cements, calcium chloride, ethylhexyl palmitate, tertiary carbonic acid glycidyl ester and chrome leather scrap hydrolysis
Residual solid is uniformly mixed, and obtains mixture A；
2) compositional liquor to be poured into blender in proportion, stirring generates foam, then mixture A poured into foam, after
Continuous stirring is poured into mold until mixture A is uniform with foams mix, defoams, surface is smoothed out.
Preferably, the acylating reagent is any one of phosphorus trichloride, phosphorus oxychloride and thionyl chloride.
Preferably, surfactant described in step (3) be Cocoamidopropyl betaine, sodium lauroyl sarcosine, ten
Any one of dialkyl benzene sulfonic acids sodium and peg-120 methyl grape sugar dioleate.
The technical advantages of the present invention are that:
(1), the present invention is when handling chrome leather scrap using sodium hydroxide, benzamide and D-sorbite cooperation
Hydrolyzation system can control hydrolyzate number-average molecular weight in 10,000 Da to 100,000 Da for being conducive to improve foaming agent comprehensive performance
Between.This method is that prior art calcium oxide or calcium hydroxide method for hydrolysis can not be accomplished.
(2), rosin is ground, the specific surface area for being conducive to rosin increases, and is dissolved rosin using benzene, is added
Acylating reagent phosphorus trichloride, phosphorus oxychloride and thionyl chloride, are sufficiently mixed rosin with acylating reagent, free in hydrolyzate
Amino reacts with acyl chlorides, is acidified solution, is conducive to control suitable pH, enables the reaction smooth reaction.
(3), it is to improve the foam performance of rosin acyl polypeptide foaming agent using surfactant A and lauryl alcohol purpose, and
Substance B, which is added, improves the half-life period of the rosin acyl polypeptide surfactant, and the frothing capacity of the foaming agent of synthesis can be with just
Beginning foam volume indicates, if the higher i.e. volume of initial foam height is bigger, illustrates that foamability is better；Half-life period is
The time consumed by the initial foam height disappearance half, if the foam stabilizing ability of the half-life period longer foaming agent for illustrating synthesis
Better, n-isopropyl acrylamide, dimethylphosphite increase separately foaming height and the half-life period of substance B, that is, enhance
Compound the two property of foaming agent.
(4), anhydrous calcium chloride plays the effect of early strength agent, and foaming agent is stirred first, it is therefore intended that foam is uniform
Stablize, contracts with gangue, 42.5 class g cements (compression strength 42.5Mpa), calcium chloride and ethylhexyl palmitate, versatic acid
The remaining chromium slag of water glyceride and hydrolysis institute is uniformly mixed, and ethylhexyl palmitate reduces water absorption rate in gangue foam concrete.
It is to improve the intensity of gangue foam concrete using the purpose of tertiary carbonic acid glycidyl ester, since shavings hydrolyzes middle part again
The residue for dividing chrome leather scrap, is baked to can be used for gangue foam concrete, reaches shavings fully- depleted, without secondary pollution
Effect.
(5), comprehensive advantage of the invention is the fully- depleted of shavings, gangue, without secondary pollution, reaches the money of waste
Sourceization utilizes purpose.
Specific embodiment
Below with reference to embodiment and comparative experimental data, the present invention will be described in detail.
Example one
(1), chrome leather scrap hydrolyzes: by shavings, drying to constant weight, then takes chrome leather scrap 100g in three-necked flask, then plus
Enter sodium hydroxide 11% (1.1g sodium hydroxide, on the basis of chrome leather scrap, similarly hereinafter), benzamide 0.2g and D-sorbite
0.1g, 8 times of water (800g water), in the case where being stirred to react under temperature 70 C hydrolysis 5h, cool to room temperature, pass through centrifugation point
It from obtaining hydrolyzate A, then filters to obtain more stable hydrolyzate B through vacuum decompression, and it is standby to hydrolyze remaining residual solid drying
With；
(2), the foaming agent preparation of the modified shavings hydrolyzate of rosin acyl chlorides: rosin 50g is ground fine and smooth then molten with benzene 30g
It solves, phosphorus trichloride 20g is added in whipping process, time for adding 1h, insulation reaction 2h, stratification is overnight, and next day takes out
The solution rosin acyl chlorides of layer；Hydrolyzate B80g is added in five mouthfuls of flasks, is slowly added into rosin under the stirring of magnetic stirring apparatus
Acyl chlorides 30g (prepared, similarly hereinafter) maintains pH8,2h is stirred to react at 40 DEG C of reaction temperature, after the reaction was completed with concentrated hydrochloric acid tune
Saving pH is 2, to precipitate in five mouthfuls of flasks, yellow mercury oxide is obtained by filtration, is cleaned with petroleum ether 10ml, obtains rosin acyl chlorides
The foaming agent of modified shavings hydrolyzate；
(3), it compounds: rosin acyl polypeptide foaming agent 10g, the Cocoamidopropyl betaine 1g, ten that step (2) is obtained
1h is mixed in glycol 0.2g and substance B 0.2g, obtains compositional liquor.
(4), gangue foaming is handled: gangue, cement, anhydrous calcium chloride, step (3) compositional liquor are uniformly mixed, into
Row foaming processing.
The detailed step of gangue foaming processing are as follows:
1) gangue is subjected to scalping, screens out the stone of larger particles, taken the remaining baking oven that is put into dry, take drying
Gangue 20g, 42.5 class g cement 775g, calcium chloride 5g and ethylhexyl palmitate 1.4g, tertiary carbonic acid glycidyl ester 2.5g,
Chrome leather scrap hydrolysed residue solid 5.6g is uniformly mixed, and obtains mixture A；
2), step (3) compositional liquor 200g is poured into blender, pulls pull rod, stirs 1.5min, by the mixed of step (1)
It closes object A to pour into foam, continues to stir, until mixture A and foams mix are uniform, uniformly mixed object is poured into mold, is disappeared
Bubble, surface is smoothed out, do foamed concrete for the gangue with glass bar.
Wherein substance B the preparation method comprises the following steps: pentaerythrite 10g is added in three-necked flask, then into three-necked flask plus
Enter maleic anhydride 1.2g and 0.4g sodium methoxide, 1h is reacted at 60 DEG C, then n-isopropyl acrylamide is added into three-necked flask
0.4g, dimethylphosphite 0.6g, are stirred to react 1h at 70 DEG C, obtain substance B.
Example two
The foam concrete preparation method utilized based on process hides chrome leather scrap and gangue comprising following process: shavings
Hydrolysis, the modified shavings hydrolyzate of rosin acyl chlorides preparation, compounding, gangue foaming processing；Detailed process is as follows
(1), chrome leather scrap hydrolyzes: by shavings, drying to constant weight, takes chrome leather scrap 100g in three-necked flask, adds hydrogen
Sodium oxide molybdena 15% (15g), benzamide 0.2g and D-sorbite 0.1g, are stirred under reaction in temperature by 12 times of water (1200g)
Hydrolysis 7h, cools to room temperature at 90 DEG C, filters to obtain relatively surely by being centrifugally separating to obtain hydrolyzate A, then through vacuum decompression
Fixed hydrolyzate B, and remaining residual solid will be hydrolyzed and be dried for standby；
(2), the foaming agent preparation of the modified shavings hydrolyzate of rosin acyl chlorides: rosin grinding 50g is fine and smooth then molten with benzene 30g
It solves, phosphorus oxychloride 25g is added in whipping process, time for adding 1h, insulation reaction 3h, stratification is overnight, and next day takes out
The solution rosin acyl chlorides of layer；Hydrolyzate B80g is added in five mouthfuls of flasks, is slowly added into rosin under the stirring of magnetic stirring apparatus
Acyl chlorides 40g maintains pH10, is stirred to react 3h at 60 DEG C of reaction temperature, and adjusting pH with concentrated hydrochloric acid after the reaction was completed is 2, to five mouthfuls
It is precipitated in flask, yellow mercury oxide is obtained by filtration, cleaned with petroleum ether 15ml, obtain the modified shavings hydrolyzate of rosin acyl chlorides
Foaming agent；
(3), compound: by the foaming agent 10g sodium lauroyl sarcosine 5g of the modified shavings hydrolyzate of step (2) rosin acyl chlorides,
2h is mixed in lauryl alcohol 0.2g and substance B 0.3g, obtains the compositional liquor.
(4), gangue foaming is handled: gangue, cement, anhydrous calcium chloride, step (3) compositional liquor is uniform, it is sent out
Bubble processing.
The detailed step of gangue foaming processing are as follows:
(1), gangue is subjected to scalping, screens out the stone of larger particles, taken the remaining baking oven that is put into dry, take drying
Gangue 200g, 42.5 class g cement 595g, calcium chloride 5g and ethylhexyl palmitate 1.4g, tertiary carbonic acid glycidyl ester
2.5g, chrome leather scrap hydrolysed residue solid 5.6g are uniformly mixed, and obtain mixture A；
(2), step (3) compositional liquor 300g is poured into blender, pulls pull rod, 1.5min is stirred, by step (1)
Mixture A is poured into foam, continues to stir, until mixture A and foams mix are uniform, uniformly mixed object is poured into mold,
Defoaming, surface is smoothed out, do foamed concrete for the gangue with glass bar.
The preparation method of substance B is pentaerythrite 10g to be added in three-necked flask, then horse is added into three-necked flask
Carry out acid anhydrides 1.2g and 0.4g sodium methoxide, 2h is reacted at 60 DEG C, then N- N-isopropylacrylamide is added into three-necked flask
0.4g, dimethylphosphite 0.6g, are stirred to react 3h at 80 DEG C, obtain substance B.
Example three
The foam concrete preparation method utilized based on process hides chrome leather scrap and gangue comprising following process: shavings
Hydrolysis, the modified shavings hydrolyzate of rosin acyl chlorides preparation, compounding, gangue foaming processing；Detailed process is as follows:
(1), chrome leather scrap hydrolyzes: by shavings, drying to constant weight, takes chrome leather scrap 100g in three-necked flask, adds hydrogen
Sodium oxide molybdena 13% (13g), formamide 0.2g and D-sorbite 0.1g, are stirred under reaction in temperature 80 by 10 times of water (1000g)
Hydrolysis 6h at DEG C, cools to room temperature, by being centrifugally separating to obtain hydrolyzate A, then through vacuum decompression filters to obtain more stable
Hydrolyzate B, and remaining residual solid will be hydrolyzed and be dried for standby；
(2), the foaming agent preparation of the modified shavings hydrolyzate of rosin acyl chlorides: rosin grinding 50g is fine and smooth then molten with benzene 30g
It solves, thionyl chloride 22.5g, time for adding 1h, insulation reaction 2.5h is added in whipping process, stratification is overnight, and next day takes
The solution rosin acyl chlorides on upper layer out；Hydrolyzate B80g is added in five mouthfuls of flasks, is slowly added under the stirring of magnetic stirring apparatus
Rosin acyl chlorides 35g maintains pH9, is stirred to react 2.5h at 50 DEG C of reaction temperature, and adjusting pH with concentrated hydrochloric acid after the reaction was completed is 2,
To be precipitated in five mouthfuls of flasks, yellow mercury oxide is obtained by filtration, is cleaned with petroleum ether 12.5ml, obtains the modified leather of rosin acyl chlorides
Consider the foaming agent of hydrolyzate to be worth doing；
(3) it compounds: by step (2) rosin acyl polypeptide surfactant 10g, neopelex 3g, lauryl alcohol
1.5h is mixed in 0.2g and substance B 0.25g, obtains the compositional liquor.
(4) gangue foaming is handled: gangue, cement, anhydrous calcium chloride, step (3) compositional liquor are uniformly mixed, into
Row foaming processing.
The detailed step of gangue foaming processing are as follows:
(1), gangue is subjected to scalping, screens out the stone of larger particles, taken the remaining baking oven that is put into dry, take drying
Gangue 110g, 42.5 class g cement 660g, calcium chloride 5g and ethylhexyl palmitate 1.4g, tertiary carbonic acid glycidyl ester
2.5g, chrome leather scrap hydrolysed residue solid 5.6g are uniformly mixed, and obtain mixture A；
(2), step (3) compositional liquor 250g is poured into blender, pulls pull rod, 1.5min is stirred, by step (1)
Mixture A is poured into foam, continues to stir, until mixture A and foams mix are uniform, uniformly mixed object is poured into mold,
Defoaming, surface is smoothed out, do foamed concrete for the gangue with glass bar.
The preparation method of substance B is pentaerythrite 10g to be added in three-necked flask, then horse is added into three-necked flask
Carry out acid anhydrides 1.2g and 0.4g sodium methoxide, 1.5h is reacted at 60 DEG C, then n-isopropyl acrylamide is added into three-necked flask
0.4g, dimethylphosphite 0.6g obtain substance B in 75 DEG C of reaction 2h.
The present invention is further illustrated below with reference to test comparison data.
Survey compression strength (7 days), Absolute Dry Density and the water absorption rate ability indirect measure concrete properties of concrete.
1 example test data of table
| Example one | Example two | Example three | |
| Compression strength/Mpa | 29.8 | 31.2 | 29.4 |
| Absolute Dry Density/kg/m3 | 0.82 | 0.86 | 0.91 |
| Absorptivity/% | 24 | 26 | 19 |
As can be found from Table 1, the compression strength of the foamed concrete prepared by the present invention, Absolute Dry Density, water absorption rate are aobvious
Show relatively good.
2 comparative example compression strength of table and absorption rate testing data
From table 2 it can be seen that not adding the compression strength of tertiary carbonic acid glycidyl ester reduces, and palm acid ethyl is not added
The absorptivity of own ester improves, and display tertiary carbonic acid glycidyl ester improves the compression strength of foam concrete, and palm acid ethyl oneself
Ester has a significant impact absorptivity, for foam concrete, needs stronger compression strength and relatively low absorptivity.
The property (compounding) of the foaming agent of the modified shavings hydrolyzate of 3 rosin acyl chlorides of table
| Example one | Example two | Example three | |
| Bubble height/mm | 125 | 165 | 153 |
| Half-life period/s | 760 | 810 | 860 |
From table 3 it can be seen that measuring the property of the foaming agent of hydrolyzate with bubble height and half-life period, found from table,
The two property is preferable.
The property (compounding) of the foaming agent of the modified shavings hydrolyzate of 4 rosin acyl chlorides of table compares (substance is not added)
The bubble height of foam performance is measured again and has change in terms of half-life period from table 4, it can be seen that substance B is not added
Change, that is, reduce the performance of substance, that is, n-isopropyl acrylamide, dimethylphosphite reduce the foaming of substance
Height and half-life period.
Molecular weight (number is equal) comparison of 5 hydrolyzate of table
As can be seen from Table 5, benzamide and D-sorbite control molecular weight are again between 1 ten thousand to 10 ten thousand, and are not added
The molecular weight for stating substance is uncontrollable, and the necessity of above-mentioned substance is added in display.
The stone of larger particles described in the detailed step (1) of gangue foaming processing of the present invention, refers to that partial size is more than
The stone of 100 mesh.
Claims (4)
1. the foam concrete preparation method utilized based on process hides chrome leather scrap and gangue comprising following process: shavings
Hydrolysis, the preparation of the modified shavings hydrolyzate of rosin acyl chlorides, compounding, gangue foaming processing；
Detailed process is as follows:
(1), chrome leather scrap hydrolyzes: chrome leather scrap being weighed as after drying to constant weight to the weight calculation radix of this step (1), puts into band
In the reaction vessel of agitating device and temperature control device, sodium hydroxide 11% ~ 15%, benzamide 0.2% ~ 0.3%, D-sorbite is added
0.1% ~ 0.2% and water 800% ~ 1200%, 5 ~ 7h is stirred to react at 70 ~ 90 DEG C of temperature, room temperature is cooled to, by being centrifugated
To hydrolyzate A, then filter to obtain hydrolyzate B through vacuum decompression, and remaining residual solid will be hydrolyzed and be dried for standby；
(2), it the foaming agent preparation of the modified shavings hydrolyzate of rosin acyl chlorides: is dissolved after rosin is ground with benzene, is added with stirring pine
The acylating reagent of fragrant quality 40% ~ 50%, 2 ~ 3h of insulation reaction, stratification is overnight, and the rosin acyl chlorides that next day takes out upper layer is molten
Liquid；
By in the reaction vessel of the hydrolyzate B investment with agitating device and temperature control device of step (1) preparation, it is added with stirring hydrolysis
The rosin solution of acid chloride of liquid B mass 35% ~ 50% is stirred to react 2-3h at 40 ~ 60 DEG C of reaction temperature, then with concentrated hydrochloric acid tune
Saving pH is 2, and yellow mercury oxide is obtained by filtration, is cleaned with petroleum ether, obtains the foaming agent of the modified shavings hydrolyzate of rosin acyl chlorides；
(3), it compounds: foaming agent, surfactant, lauryl alcohol and substance B that step (2) is obtained, according to mass ratio 100:
(10 ~ 50): (1 ~ 3): 1 ~ 2h is mixed in (2 ~ 3), obtains compositional liquor；
Wherein, substance B the preparation method comprises the following steps: pentaerythrite, season are added in the reaction vessel with agitating device and temperature control device
The maleic anhydride of penta tetrol quality 10% ~ 15% and the sodium methoxide of pentaerythrite quality 3% ~ 5% react 1 ~ 2h at 55 ~ 65 DEG C,
The n-isopropyl acrylamide of pentaerythrite quality 3% ~ 5% and the dimethylphosphite of pentaerythrite quality 5% ~ 8% are added,
It is stirred to react 1 ~ 3h at 70 ~ 80 DEG C, obtains substance B；
(4), foam concrete prepare: by gangue, cement, calcium chloride, ethylhexyl palmitate, tertiary carbonic acid glycidyl ester,
And the residual solid of drying that step (1) obtains is after mixing, and the compositional liquor that step (3) obtain is added, continues to stir, obtain
To the foam concrete utilized based on process hides chrome leather scrap and gangue；
Wherein, the drying that gangue, cement, calcium chloride, ethylhexyl palmitate, tertiary carbonic acid glycidyl ester, step (1) obtain
Residual solid and the obtained compositional liquor of step (3) between mass ratio are as follows: (20 ~ 200): (595 ~ 775): (3 ~ 8): (1 ~
2): (2 ~ 3): (5 ~ 10): (200 ~ 300).
2. the foam concrete preparation method utilized as described in claim 1 based on process hides chrome leather scrap and gangue, special
Sign is step (4) specific practice:
1) gangue, is subjected to scalping, screens out the stone of larger particles, takes the remaining baking oven that is put into dry, takes drying in proportion
Gangue, 42.5 class g cements, calcium chloride, ethylhexyl palmitate, tertiary carbonic acid glycidyl ester and chrome leather scrap hydrolysed residue
Solid is uniformly mixed, and obtains mixture A；
2) compositional liquor is poured into blender in proportion, stirring generates foam, then pours into foam mixture A, continues to stir
It mixes, until mixture A uniform with foams mix, is poured into mold, defoams, surface is smoothed out.
3. the foam concrete preparation method utilized as described in claim 1 based on process hides chrome leather scrap and gangue, special
Sign is that the acylating reagent is any one of phosphorus trichloride, phosphorus oxychloride and thionyl chloride.
4. the foam concrete preparation method utilized as described in claim 1 based on process hides chrome leather scrap and gangue, special
Sign is that surfactant described in step (3) is Cocoamidopropyl betaine, sodium lauroyl sarcosine, detergent alkylate sulphur
Any one of sour sodium and peg-120 methyl grape sugar dioleate.
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| CN110698141A (en) * | 2019-11-08 | 2020-01-17 | 中电建路桥集团有限公司 | Composite foam light soil and preparation method thereof |
| CN111205015A (en) * | 2020-01-20 | 2020-05-29 | 东南大学 | Preparation method of high-stability foam concrete foaming agent |
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| CN113527719B (en) * | 2021-07-29 | 2022-11-08 | 陕西科技大学 | Preparation method of high-strength nano composite three-network hydrogel based on waste chrome leather scraps |
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| CN113060992A (en) | 2021-07-02 |
| CN110183155B (en) | 2021-04-30 |
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