Method of obtaining foam-generator for foam-concrete constructions

FIELD: chemistry.

SUBSTANCE: invention relates to a method of obtaining ampholytic surface-active substances on the basis of a protein-containing raw material and can be used in the process of production of foam-concrete and foam-concrete constructions. In the method of obtaining a foam-generator for the production of foam-concrete and foam-concrete constructions, including the hydrolysis of the protein-containing raw material in the presence of calcium hydroxide, calcium hydroxide is formed, when calcium oxide is introduced in a hydrolysed reaction mixture, the hydrolysis process is carried out in one stage in a reactor-hydrolyser, provided with high-speed stirrer and an external circular loop with a pump for 5-9 hours at a temperature of 110-132°C with the weight ratio of initial ingredients "feather wastes:water:calcium oxide", equal to 100 : (350-400) : (3.5-3.7), with pH of the lime-feather mass at the beginning of hydrolysis varying within the interval of 12.0-12.4, and at the end of hydrolysis in the interval of 7.5-7.7.

EFFECT: obtaining the foam-generator with high foam-generating properties, which are achieved both with the application of moderately mineralised water and alkaline highly hard lime water.

1 ex, 1 tbl

 

The invention relates to a method for ampholytic surface-active agents (surfactants) on the basis of protein-containing raw material and can be used in the production of foam concrete and foam concrete structures.

It is known that most of the SAS are good foamers. However, their high foaming properties occur in brackish water and neutral pH values. Our research has shown that regardless of the adopted by the builders of the ratios of sand : Portland cement", the pH environment of these sand-cement compositions is in the range of 12.2 and 12.4. This is because the mixing of water-Portland cement, along with hydrates clinker materials, hydration 3-calcium silicate and 4-calcium silicate almateria reactive calcium hydroxide. Therefore, used for the production of concrete of the surfactant should have a high foaming properties in a strongly alkaline medium and in the presence of calcium cations, i.e. in very hard water.

Testing of all major typical surfactants: primary and secondary alkyl sulphates, alkyl - and alkylarylsulfonates, neonols, cationic surfactant cetylpyridium chloride), reincorporate, sulfosalicylate, showed that only products of sulfonation of certain fractions of the olefins have in alkaline lime is Oh water high foaming properties, that is explained by the presence in their structure of hydroxyl groups and multiple bonds. However, the practical application of these surfactants-foam hampered by economic considerations, because of their relatively high cost.

Surfactant-foaming agents for foamed concrete are large tonnage production and therefore they should be very cheap and for their production should be applied available and cheap raw materials or, preferably, man-made waste. Moreover, the production technology of such surfactants should be simple.

The known method according to the patent of the Russian Federation 2141930, publ. 27.11.1999, which is as follows. To dry proteinogram substance microbial synthesis add lime, water, and the resulting mixture was heated with stirring in a period of time necessary to achieve optimum foaming activity - ratio and durability. After hydrolysis, the mixture is cooled to room temperature and filtered. The filtrate is injected salt of metal (for example, Fe2(SO4)3, FeSO4, FeCl3, CuSO4and others). The resulting solution after 10-fold dilution water has foam 10-17, stability 12-14 h and can be used as a foaming agent. The disadvantage of this method is its narrow specific focus on ispolzovaniyu.

It is known that in the manufacture of foam concrete can be used foaming agents derived from protein-containing waste. For example, based on the blood of animals ("Processing the blood of slaughtered animals". - Agropromizdat, 1988, S. 212-214).

The greatest interest as a raw material for foam are keratin scleroprotein, such as horns, hooves, scales of fish, feather waste.

From a chemical point of view keratin wastes differ from other fibrillar structural protein content of a large number of cystine, cestina and methionine, and therefore, a stable sulfide and polysulfide fragments. Keratin scleroprotein inert, they are not soluble either in water or in solutions of weak acids and alkalis or organic solvents. However, with increasing temperature is slow hydrolytic destruction of the peptide, sulfide, polysulfide linkages and acid amide groups. In the inert polymers-keratins are transformed into water-soluble oligomers-polypeptides. Catalyzed hydrolysis process as acids and bases.

A method of refining rogakopita waste by RF patent 2206543, publ. 20.06.2003 g, where dried relocatee raw materials corresponding to GOST 18253-72, razvarivat in aqueous sodium hydroxide solution when the temperature is e 85°C for 6 hours. At steady state in a copper pour sodium fluoride, which is antiseptic. After hydrolysis, the solution is cooled to room temperature and filtered to separate the undissolved residue. The resulting solution was neutralized ammonium chloride to pH 7.5 and stabilize iron sulfate. To obtain a foam blowing agent is dissolved in water in the amount of 2-6% by weight of water, depending on the generator, then an aqueous solution of the foaming agent is transformed into a stable foam multiplicity 6-14. The disadvantage of this method is its narrow specific focus on raw materials used and not high enough ratio of the obtained foam.

The known method of using rogakopita waste (RF patent 2206543, publ. 20.06.2003 year), the Lack of which is that specified by the foaming agent can be obtained only low expansion foam when you use a sufficiently concentrated (5%) of the foaming agents in the water.

There is a method of using the protein-containing raw material (RF patent 2288203, publ. 27.11.2006,), the lack of which is the fact that the foaming agent allows to obtain the desired foam quality from fairly concentrated (5%-s) water solutions.

Closest to the developed method is a patent of the Russian Federation 2395471, published the 11.04.2008 g, according to which way to get the foaming agent consists of two stages:

- hydrolysis for 0.5-10 hours protein-containing raw material in the form of a pen hydrolysis of flour at a temperature of 75-106°C in the presence of a large quantity of alkali, such as sodium hydroxide, potassium, calcium or ammonium,

- neutralize the excess alkalinity of sulphuric acid.

Then bring in the neutralized hydrolyzate of iron sulfate (ΙΙ) and the organic solvent, with subsequent sedimentation during the day.

The disadvantages of the prototype can be attributed to the need to use raw materials in the form of a pen hydrolysis flour, which is produced by steaming raw protein-based pen poultry waste, which increases the cost and reduces the raw material base of production; a process in two stages - first the hydrolysis of pen hydrolysis of flour with a large amount of alkali, and then neutralizing the excess alkalinity of organic or inorganic acids which do not form water-insoluble compounds with cations of iron, Fe2+acid salts of these acids or salts that lower pH due to chemical reactions with components of the hydrolysate; and using the formula foaming agents iron sulfate (ΙΙ) and an organic solvent, which generally complicates and increases the cost of technology in Addition, the disadvantage is the reduction of the blowing performance of the obtained foam using water with a high hardness due to the formation of calcium sulphate by neutralizing excess alkalinity and then when the exchange reaction of sodium sulfate with calcium hydroxide in concrete.

The basis of the invention is to provide a method for obtaining a foaming agent for foam concrete structures based on the pen poultry waste, free from the disadvantages of the prototype.

Technical result: high foaming properties foaming agent, which is achieved as when using moderately saline water and alkaline high rigid lime water.

For example, in the case of using tap water foaming properties foaming agent obtained by the proposed method when the concentration of the foaming agent, equal to about 0.6 wt.%, correspond to the properties of the foam obtained by the prototype, when the concentration of the foaming agent to 3.0 wt.%

When using lime water at pH 12.2 and total hardness ~500 mmol/liter, which corresponds to the real conditions prevailing in the production of foam concrete, multiplicity and stability factor of the foam blowing agent prototype is almost two times less than the ratio and coefficient stability and foam blowing agent such as concentration, obtained by the proposed method.

In addition, the process of getting foam on the proposed method can be implemented using as raw material directly down waste poultry farms, is one and does not require any in his recipe ingredients.

The proposed method for foaming agent includes the hydrolysis of protein-containing raw material in the presence of calcium hydroxide and, unlike the prototype, contains the following new features:

as a protein-containing raw materials use pen poultry waste,

- hydrolysis of feather waste poultry carry out intensive hydrodynamic dispersion at a temperature 110-132°C for 5-9 hours, while calcium hydroxide is formed by the introduction of gidrolizuyutza the reaction mixture of calcium oxide,

the ratio of ingredients by weight "pen waste : water : calcium oxide respectively equal to 100 : (350-400) : (3,5-3,7) ,

- pH lime-down weight at the beginning of hydrolysis in the range of 12.0 and 12.4, and by the end of hydrolysis in the range of 7.5 to 7.7,

- effective hydrodynamics dispersion and mass transfer is due to the fact that the reactor-hydrolizer equipped with high-speed stirrer and connected to the external circular path, and the circulation is carried out by the pump.

according to our research, most high foaming properties of the hydrolysates obtained with the use as catalyst of calcium hydroxide, in comparison with analogues, obtained by using as catalysts for sulfuric and phosphoric acids, caustic soda and caustic potash, and soda ash.

In addition, the cause of increased foaming properties foaming agent, in comparison with the prototype, due to the fragmented structure of the polypeptide oligomers. With an excess of strong alkali used according to the prototype, there is a chaotic spontaneous destruction of the peptide bonds of macromolecules keratin. The result is a significant variation in the molecular weight of the polypeptide relative to their average value.

Optimal surface-active properties of the polypeptides containing about 8-12 amino acid fragments. The deviation from this value as downward and upward, resulting in reduced surface-active, and hence foaming properties.

To optimize polypeptide granular composition in the present invention provides for the hydrolysis of feather waste at the optimum temperature and most importantly at the optimum weight ratio of "pen waste : calcium oxide". Acknowledgements the om strict compliance with the optimality of this ratio is the change in initial pH, which before hydrolysis lime-feather weight in the range pH to 12.0 and 12.4, to the value at the end of hydrolysis in the range pH 7.5 to 7.7, which is close to the isoelectric point.

The process of hydrolysis during the first hours of proceeds as in a heterogeneous system "liquid - solid pen substance", and in the diffusion region. Formed on the surface of a solid keratin substance is a water-soluble polypeptides diffuse in the liquid alkaline phase, where continue to either hydrolyzed to smaller fragments. At the same time, macromolecules located in the nucleus keratin solid particles for a long time not undergo a process rosepetallove hydrolysis. Therefore, due to differences in time of chemical exposure in respect of superficial and deeper of protein molecules is a significant variation in fragmented composition of the oligomeric polypeptides - differential heterogeneous irregularity (DGN).

To fully get rid of this phenomenon is impossible, but to reduce its consequences. To this end, the invention provides a process of hydrolysis with effective hydrodynamics by applying a high-speed stirring; the reactor-hydrolyzer is connected to the external circular path, and the circulation is carried out by the pump. This allows for near the local hydrodynamic pressure effectively "remove" the superficial layers of swelling of the keratin and dispersing them in the volume of the reaction medium to nanosized particles. Thereby intensified mass transfer and purely heterogeneous system becomes more and more homogeneous and, therefore, reduces the effect DGN.

Specific example

As a protein-containing raw materials use pen poultry waste in the form of feather meal, can also be used and pen hydrolysis flour.

In the reactor-hydrolizer, equipped with high-speed stirrer and connected to the external circular loop with a pump, enter ingredients: feather waste, water and calcium oxide in a ratio of 100 : (350-400) : (3,5-3,7) respectively. In the reaction mixture is formed calcium hydroxide, at this pH, lime-down weight at the beginning of hydrolysis equal to 12.0 and 12.4. The hydrolysis is carried out at a temperature 110-132°C for efficient hydrodynamics by stirring the reaction mixture turbine or any other high-speed stirrer and circulation of the reaction mixture due to the connection of reactor-hydrolyzer to the external circular contour, provided with a pump, for example a vortex.

The process of hydrolysis are for 5-9 hours until the value of pH of 7.5 to 7.7. The table below indicates the comparative quality indicators foam obtained according to this invention and prototype.

Table
№ p/pThe method of producing foamFoaming properties of solutions foam
Water used in the preparation of R-RA foamConcentric, wt.%Foam2)The stability factor3)
1According to prototypeTap water, total hardness 7.2 mmol/liter3,010,9-12,10,97-0,99
2-//--//-0,6of 7.1-8.20,82-0,9
3-//-Lime water1)total hardness ~500 mmol/liter, pH of 12.23,07,2-7,50,83-0,88
4-//--//-0,66,2-6,70,8-0,82
5According to the inventionTap water, total hardness 7.2 mmol/liter3,015,7-18,10,97-0,99
6-//--//-0,611,9-12,10,96-0,98
7-//-Lime water1)total hardness ~500 mmol/liter, pH of 12.23,0of 13.2 to 13.90,98-0,99
8-//--//-0,610,5-11,10,96-0,98

Notes:1)Lime water was prepared from tap water saturation excess of calcium oxide to pH of this water 12,2 corresponding to the normal alkalinity of cement mortars, where typically the pH is 12-12,4.

2)The ratio of the foam was determined as the ratio of the volume of foam obtained from 100 ml of a solution of foaming agent dispersion for one minute in the mixing probyvala, to 100 ml of the original solution

3)The foam stability factor defined as the ratio of volume of foam concrete mass obtained by mixing for one minute of equal volumes of cement paste (water / cement ratio water/cement = 0,45), and foam, to the sum of the initial volumes of cement paste and foam.

Tests of 3.0 wt.%-aqueous foaming solution, obtained according to the prototype, using tap water of moderate hardness, showed its high quality and confirmed the findings of the prototype (experiment 1). However, at lower concentrations with 3.0-x to 0.6 wt.%, as a ratio, and the coefficient of resistance is markedly lowered their values (experiment 2). In lime water to 0.6 wt.%-nye and even 3.0 wt.%-these solutions foam prototype further reduce their quality indicators, which are not fully comply with the requirements (experiments 3 and 4, the foam ratio of 6.2 and 7.5, and the foam stability factor 0,78-0,88). For reference: foaming agent for foam concrete meets the requirements when the value of the ratio of foam and its stability is not less than 8.0 and 0.95, respectively.

Compared with the prototype, the foam obtained according to the proposed invention, on the basis of tap water, and lime water, has a higher performance (experiments 5-8). Even indicators of 0.6 wt.%-different solution is in strongly alkaline mineral lime water is at the level of indicators foaming ability of 3.0 wt.%-solutions prototype for neutral water of moderate hardness (experiments 1,8).

Thus, the task of creating a method of obtaining high-quality foaming agent for foam concrete structures on the basis of feather waste poultry solved by optimization of the technological process of hydrolysis and allows the following.

1. Use cheap and available raw materials - not only gidralizovanny pen flour according to the prototype, but also man-made pen poultry waste.

2. To carry out the method of producing foam in one stage, in contrast to the 2-stage prototype.

3. To save raw materials, as it eliminates the additional use of sulfuric acid, iron sulfate (ΙΙ) and an organic solvent, and due to the economy of the foaming agent, ensuring high performance even at 0.6 wt.%-Noah the concentration of the solution in strongly alkaline mineral lime water

The application of the foam obtained by the proposed method allows to reach the main of the main indicators in the manufacturing of foam concrete and foam concrete structures.

Due to the high stability of the foam pen hydrolysates in strongly alkaline environments and in relation to ions of calcium is really possible to produce high-quality light-weight foam concrete structures. This will allow consumption of Portland cement, to improve thermal insulation of buildings and the structures are built, to improve the comfort of homes by improving sound insulation and ensure the microclimate close to the microclimate of wooden buildings, as well as to address specific environmental issue is the use of waste as a cheap source of raw material.

The way to obtain a foaming agent for the production of foam concrete and foam concrete structures, including the hydrolysis of protein-containing raw material in the presence of calcium hydroxide, wherein the calcium hydroxide is formed by the introduction of gidrolizuyutza the reaction mixture of calcium oxide, hydrolysis process lead at one stage in the reactor-hydrolizer, equipped with high-speed stirrer and external circular loop with a pump, for 5-9 hours at a temperature of 110-132°C at a mass ratio of the original ingredients "pen waste : water : calcium oxide, equal 100 : (350-400) : (3,5-3,7), at this pH, lime-feather weight at the beginning of hydrolysis in the range of 12.0 and 12.4, and by the end of hydrolysis in the range of 7.5 to 7.7.



 

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