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Waste-free technologies based on caprolactam production waste
PRODUCTION OF AMMONIUM SULFATE FROM WASTE OF CAPROLACTAM PRODUCTION
waste caprolactam building inhibitor
As a result of the famous Beckmann rearrangement, cyclohexanone oxime is converted to caprolactam, a monomer for the production of nylon-6. In industrial practice, after the rearrangement is complete, the reaction mixture is neutralized and the lactam is isolated from the mixture by extraction or other suitable methods. The most commonly used neutralizing agent is ammonium hydroxide. In this case, when using sulfuric acid as a rearrangement catalyst, the by-product is ammonium sulfate, which cannot be reused in the production process. Ammonium sulphate can be marketed as a fertilizer, but this product is usually marketed in sufficient quantity and at a low price.
In addition, 3 tons of ammonium sulfate is formed per 1 ton of caprolactam produced, which creates problems with its disposal, since the production of caprolactam is constantly growing, and the prices of the by-product are low. The neutralization process consumes large amounts of water; it is exothermic and the heat generated is removed in the form of hot water and steam to maintain the temperature of the process. Large volumes of the reaction mass at the stage of neutralization cause the high cost of separating lactam from the by-product and obtaining ammonium sulfate.
Neutralization of sulfuric acid with other bases leads to the formation of even cheaper or little-used products. For example, calcium hydroxide, a cheap reagent, produces calcium sulfate in the neutralization step, which has a low market price, is insoluble, and is prone to deposits and clogged pipelines. Thus, a desirable alternative to existing production is not new methods for the neutralization and recovery of ammonium sulfate, but the development of a process that completely eliminates this problem.
A discussion about the production of caprolactam without the simultaneous formation of ammonium sulfate is presented by R. Mattone, G. Scioli and L. Gifret, Snia Viscosa, see Hydrocarbon Processing*, January 1975.
See also US Pat. No. 4,015,946 "Ammonium Sulfate from Acrylonitrile Production Effluent", which discusses the problems of processing waste from the production of caprolactam.
The invention relates to the building materials industry and can be used for the production of ceramic bricks, stones, blocks and tiles.
Known raw mixture for the manufacture of wall ceramic products, including the following components, wt. clay shales from overburden of phosphorites 74-85; clay 10-25 and sulphate mixture is a waste product of caprolactam production 1-5.
When firing bricks from this raw mixture, sulfur dioxide, chlorine and vapors of the corresponding acids are released, which are formed as a result of chemical reactions of Na 2 SO 4 and NaCl contained in the sulfate mixture with its other components. All these substances have a harmful effect on the human body, cause corrosion of technological equipment, do not allow the heat of exhaust gases to be utilized, for example, for drying raw bricks, and pollute the environment. Not decomposed, as well as formed during firing, secondary sodium sulfate is a water-soluble salt that forms efflorescence on the surface of the brick, reducing its durability and decorative properties. Sulfate and sodium carbonate contained in the sulfate mixture decompose at temperatures above 850 ° C. The reactive sodium oxide formed as a result of this decomposition, which participates in the formation of neoplasms, interacts with clay components (SiO 2, Al 2 O 3 , FeO, etc. .) only after their amorphization, i.e., at temperatures above 900 ° C. As a result, the brick firing temperature is 1000-1050 ° C. In addition, a brick from a known raw mixture has an increased density and reduced strength due to the presence of an inert (non-reactive) , having a stable crystal lattice, silicon oxide (v-quartz), interacting with other oxide mixtures at temperatures above 1050 ° C, and at a temperature of 1000-1050 ° C, it remains mainly in the form of inert inclusions and does not participate in the formation of a strong ceramic shard.
Known raw material mixture for the manufacture of ceramic products containing active silica 72.4-74.7% ash TPP 7.7-11.0% alkaline soap waste chemical production 15.3-17.6% This mixture has significant drawbacks. The presence of sulfur compounds in the ash, and in most soap production wastes, for example, soap liquors up to 10% NaCl, causes the negative phenomena described above. The components that make up alkaline soap waste do not provide the formation of polymerized particles of the colloidal composition of micelles, which contribute to the convergence of solid rock particles at the drying stage, increasing their surface of reactionary interaction during the firing process. This factor, as well as the low content of active NaOH (0.1%) in the waste, which promotes the formation of a liquid phase, predetermines the occurrence of mainly solid-phase reactions during firing, which ultimately explains the relatively low compressive strength (268-305 kg / cm 2) fired at a temperature below 1100 ° C products from this mixture. The need to conduct firing at temperatures above 1100 ° C requires increased fuel costs, as well as the cost of refractory materials for the manufacture and frequent repairs of the furnace and trolleys. The three-component composition of the mixture, in comparison with the two-component, significantly complicates the production line and increases the cost of production.
Known raw mix for the manufacture of small building products, including, by weight. diatomaceous material 64-70; limestone 10-16; soapy liquor 16-25 .
The disadvantages of this raw mixture are: increased equipment costs and energy costs associated with the need for fine grinding of diatomaceous material and limestone (before passing through a 1 mm sieve) and the complication of obtaining a homogeneous mixture of three components (the need to pass the mixture through a 1.5 mm sieve); high firing temperature of products (1100 ° C) and their relatively low compressive strength (412-466 kg / cm 2) due to loosening of the semi-finished product structure by released carbon dioxide and reactions in the solid phase; the formation of "duks" and spalls in products from the contact of active CaO with a size of more than 0.5 mm with atmospheric moisture (since limestone is ground to 1 mm, it is natural that there are particles of more than 0.5 mm in the mixture, which pass into the product during firing) ; the release of chlorine during the firing of products, the harmful effect of which has already been noted above. The closest to the recommended one is the raw mix for the manufacture of building products, including, wt. component from the group: tripoli, diatomite, flask 66-72; waste production of calcium chloride 6-12; soap liquor 20-24 .
The high content of chlorides and sulfates, which are part of the soap liquor and waste from the production of calcium chloride, has a harmful effect on people, equipment and product quality, as noted above. The release of a significant amount of gases (SO 2 , Cl, CO 2 , hydrocarbons) during the firing of products leads to the destruction of the continuity of the product, the shift of the sintering process to the temperature zone above 1000 (1120 ° C) and a decrease in strength. The content of sulfates in the mixture does not make it possible to obtain facial ceramic products from it due to efflorescence and punctures on their surface. In addition, the increased content of carbonates and sulfates in the mixture causes the formation of gelenite and anhydride in the products, which also reduce the strength of the products. The low content of free alkali (0.1%) in the soap liquor, the high content of calcium oxide in the mixture, and the release of a large amount of gases from products during firing predetermines the flow of reactions in the solid phase. The sintering of the material occurs at a high temperature, which requires high fuel consumption and increases the cost of refractory materials for furnaces and trolleys. The strength of products from mixtures specified in the prototype is also not very high in compression 498-510 kg/cm 2 and bending 15.9-29.6 kg/cm 2 .
The purpose of the invention is to reduce the firing temperature of ceramic wall products, increase their strength characteristics, utilize chemical production waste, and exclude harmful emissions into the atmosphere.
The task is achieved by the fact that the raw mix for the manufacture of building bricks, including silica-containing raw materials and caprolactam production waste, as silica-containing raw materials, it contains amorphous-siliceous rock (flask, diatomite, tripoli), and as alkaline waste, alkaline waste from caprolactam production. The use of amorphous-siliceous rock in the amount of 75-99 wt. together with alkaline effluent from the production of caprolactam (SCHSPK) in the amount of 1-25 wt. ensures the production of a dense and strong structure of raw brick as a result of the interaction of amorphous silica, which is part of the amorphous siliceous rock, with sodium salts of monodicarboxylic acids schSPK even in the process of drying the brick (100 ° C) and the formation of polymerized particles of colloidal silica micelles, enveloping solid particles contained in the rock, bringing them together and increasing the surface of the reaction interaction during the firing process. The increased density of the raw brick contributes to the prolongation of the process of burning out the organic substances of the ShchSPK and its completion in the region of elevated temperatures. When burned, organic substances create a reducing environment and porous the material (product). Active NaOH, which is 20 times (2.0% vs. 0.1%) more in ASPK than in soap liquor, and Na 2 O, the product of thermal dissociation of mono- and dicarboxylic acids ASPK, interacts with amorphous silica to form alkaline silicates: 2Na 2O? SiO2? Na2? SiO 2 and Na 2 O? 2SiO2. The reducing environment and the proximity of amorphous silica particles due to the formation of micelles, as well as the presence of other oxides (FeO, Al 2 O 3) in the composition of the mixture, contribute to the formation of a highly active sodium silicate melt at a temperature of about 600 ° C, which interacts with the solid phase, activating the process particle sintering. As a result of melt crystallization, strong minerals (albite, oligoclase, sodium ferrosilicate) are formed, which determine high strength properties of products. When the content in the mixture is less than 1% SCHSPK, the formation of the melt shifts to the region of high temperatures (>800 about C). With more than 25% content of SSPK in the mixture, an excessive amount of highly mobile (with low viscosity) melt enriched with Na 2 O is formed, which, actively reacting with crystalline silicates, destroys the structural frame of the ceramic shard, reducing its strength. Thus, the use of the proposed mixture allows to obtain high-strength products with reduced density at low firing temperatures, and the absence of harmful substances in the components of the mixture makes the process of obtaining products from the proposed mixture environmentally safe and eliminates equipment corrosion.
For the manufacture of products, Kamyshlov diatomite, Balasheykinskaya flask, tripol and SCHSPK containing sodium salts of organic acids 26.48; resins 6.80; cyclohexanol 0.009; cyclohexanone 0.008; sodium hydroxide 2.0, water 64.703. The chemical compositions of diatomite, flask and tripoli are given in table. 1. Sample preparation is carried out as follows. Amorphous-siliceous rock (diatomite, flask, tripolite) was crushed before passing through a sieve with a hole size of 3 mm, and then mixed with ASPK, which can be used in liquid form, in the form of a paste or dry form after dehydration at 100 ° C, and also after pre-calcination at 200-700°C. After mixing the components, the mixture was moistened to 15% moisture content and molded by semi-dry pressing at a pressure of 130 kg/cm 2 cylinder samples with a diameter and height of 50 mm and plates 150 x 20 x 10 mm. Molding can also be carried out in a plastic way, in which case the molding moisture will be 30%. maximum temperature for 30 minutes. The firing temperature rise rate to the maximum was 10 deg/min. The samples were cooled for 2-3 hours. Depending on the ratio of components in the mixture and the firing temperature, the samples have a color from milky white to bright red.
When the firing temperature rises above the maximum, deformation or swelling of the samples is observed, and at a temperature below the minimum, their quality indicators drop sharply. products from the proposed mixture is 300-400 ° C lower, which guarantees a significant reduction in energy costs for the production of products, an increase in the service life of furnaces and trolleys, as well as a reduction in the cost of materials for their manufacture, since the need for refractories decreases: at a lower density, and therefore, the mass strength of products from the proposed mixture is higher than that of products from mixtures specified in the prototype and analogues; no harmful substances are emitted during the firing of products.
Raw mix for the manufacture of building products
Claims of the invention: Raw mixture for the manufacture of building products, including a component from the group of tripoli, diatomite, flask and alkaline production waste, characterized in that it contains an alkaline waste from the production of caprolaclam as an alkaline waste in the following ratio of components, wt. A component from the group of tripoli, diatomite, flask 75 99 Alkaline effluent from caprolactam production (dry) 1 25
The invention relates to the field of protection of metals from corrosion and can be used in the oil and gas industry, specifically to protect oil production equipment from acid corrosion, including hydrogen sulfide. The essence of the invention: the inhibitor contains oxygen-containing waste production of caprolactam, which is used as a cube of rectification of the products of oxidation of cyclohexane and dehydrogenation of cyclohexanol or its mixture with the alcohol fraction of the production of caprolactam, and a nitrogen-containing additive, which contains monoethanolamine or nitrogen-containing waste production of ammonia or caprolactam at a mass ratio oxygen and nitrogen-containing component in a mixture of 2.5 - 1:1. 3 w.p. f-ly, 1 tab. The invention relates to the field of protection of metals from corrosion and can be used in the oil and gas industry, specifically to protect oil production equipment from acid corrosion, including hydrogen sulfide.
A large number of compositions of inhibitors of acid corrosion of metals are known from the prior art, including nitrogen-, sulfur-, phosphorus-containing and unsaturated compounds.
Of these, corrosion inhibitors produced on the basis of waste from petrochemical industries are of the greatest practical interest. The involvement of production wastes in the synthesis of inhibitors makes it possible to significantly expand the raw material base, reduce the cost, and also increase the efficiency of the main production.
Known inhibitor of atmospheric corrosion, presented on the basis of waste production of caprolactam, namely the heavy fraction obtained after vacuum separation of cyclohexanone and cyclohexanol from the distillation residue of the distillation of by-products of the oxidation of cyclohexane and dehydrogenation of cyclohexanol (oil POD).
The disadvantage of the composition is its high efficiency as an inhibitor of acid corrosion in oil environments, a large amount of waste in the production of the inhibitor, since only a part of the POD oil is used. The closest in technical essence to the invention is a composition of an inhibitor of acid corrosion in oilfield environments, containing a waste production of caprolactam and a nitrogen-containing additive. Large volumes of consumption of acid corrosion inhibitors in the oil and gas and oil refining industries dictate the need to develop an inhibitor composition that is characterized by high protection efficiency, low production cost, and availability of raw materials.
This goal is achieved in that the acid corrosion inhibitor in oilfield environments contains oxygen-containing waste products of caprolactam production and a nitrogen-containing organic additive, and these wastes contain a cube of rectification of the products of cyclohexane oxidation and dehydrogenation of cyclohexanol or its mixture with an alcohol fraction of caprolactam production, taken in a mass ratio of 4:1 , and as a nitrogen-containing additive - monoethanolamine or ammonia production waste, or caprolactam at a mass ratio of oxygen and nitrogen-containing components in a mixture of 2.5-1: 1. waste from the production of ammonia, the distillation residue of monoethanolamine gas purification is used, and as a waste from the production of caprolactam, the distillation product of the caprolactam production is used.
A comparative analysis with the composition of the prototype allows us to conclude that the proposed composition of the corrosion inhibitor differs from the known one by the introduction of new components, namely, as an oxygen-containing waste from the production of caprolactam, a cube of rectification of the products of oxidation and dehydrogenation of cyclohexanol (POD oil), a mixture with an organic solvent - an alcohol fraction production of caprolactam (SPPC), taken in a mass ratio of 4:1. As a nitrogen-containing additive, monoethanolamine or nitrogen-containing wastes from the production of ammonia (distillation residue of monoethanolamine gas cleaning) or caprolactam (distillation residue of caprolactam distillation) were used.
Thus, the claimed technical solution meets the criterion of "novelty".
An analysis of the known compositions of acid corrosion inhibitors showed that some of the components introduced into the proposed formulation are known, however, their inhibitory functions are poorly expressed (see table, examples 2 and 3).
At the same time, special studies carried out in the latter case proved that the anti-corrosion properties of POD oil as an individual component, as well as when it is mechanically introduced into the formulation of a paint and varnish coating, practically do not appear. The protective properties of POD oil are manifested only when using a special technology for its introduction into the composition.
The components of the proposed formulation form a synergistic mixture that can significantly improve the effectiveness of corrosion protection in various oilfield environments. Thus, based on the foregoing, we can conclude that the proposed solution meets the criterion of "inventive step". As a result of the implementation of the invention, the following technical and socio-economic effect is achieved. The proposed inhibitor provides high efficiency of corrosion protection in hydrocarbon, water, and two-phase media in a wide temperature range of use (from -40 to +60°C); The production of the inhibitor is based on an available raw material base, including large-tonnage production waste that is not currently being used qualified. This makes it possible to significantly reduce the cost of producing an inhibitor relative to known analogues (cheap raw materials, organizing production at the location of raw materials, saving energy resources for waste disposal, etc.), and at the same time significantly improve the technical and economic efficiency of the main production (caprolactam); the qualified use of the main large-tonnage wastes of caprolactam production significantly improves the economic performance of the technology.
For experimental verification of the proposed inhibitor composition, 16 samples were prepared, 8 of which showed optimal results. The results are presented in the table of examples. As oxygen-containing wastes from the production of caprolactam, "POD oil" was used, corresponding to TU 113-03-476-89 or its mixture with the alcohol fraction of caprolactam production (SFPC), corresponding to TU 113-03-10-5-85 . POD oil is a residue of rectification of the products of cyclohexane oxidation and cyclohexanol dehydrogenation. The product contains esters of carboxylic acids, volatile components (low molecular weight alcohols and aldehydes), cyclohexanol, cyclohexanone, cyclohexylidene-cyclohexanol, heavy high-boiling products of polycondensation and polymerization. The introduction of SFPK into the composition in the ratio of oil POD: SFPK = 4:1, along with improving the effectiveness of protection, can significantly improve the performance characteristics of the formulation, expand the temperature range of its application (see examples 10 and 12).
As a nitrogen-containing organic additive, either monoethanolamine (TU 6-02-915-84) or nitrogen-containing wastes from the production of ammonia or caprolactam, specifically the bottom residue of monoethanolamine purification of gases from ammonia production (having the composition, wt.%: monoethanolamine 40-80, water 15 -50, impurities 5-15), which is currently being burned, or the bottom product of caprolactam distillation, corresponding to TU 113-03-10-6-84.
To reduce the viscosity of the inhibitor, an additive of a surfactant such as oxyethylated alkylphenols, for example, OP-7 or OP-10, can also be introduced into its composition. The specified additive can be introduced into the composition in an amount of up to 5 wt.% of the weight of the inhibitor.
The inhibitor is obtained by simple mixing of the ingredients at a temperature of 20-60°C and a stirring time of 2-4 hours. The optimal concentration of the inhibitor in the water-oil emulsion is 50-200 mg/l.
The inhibitory properties of the proposed inhibitor were tested according to the standard method (GOST 9.506-87, section 2 of OST 14-15-15-7-85) with the following changes:
flat samples (plates) of steel St. were used as control samples. 3 according to GOST 380-91, size 50x20x2 mm, with holes at one end with a diameter of 4 mm;
as a reaction medium, a highly mineralized oilfield medium from the production company "Kuibyshevneft" was used, with the following characteristics: hydrogen sulfide content from 140 to 600.0 mg/l, pH 5.4-6.2, density 1.025-1.162 g/cm3, degree of mineralization 100 -250 g/l, as well as NaCE medium; hydrogen sulfide content 1156 mg/l, pH 3.35;
tests were carried out by gravimetric and electrochemical methods in dynamic mode;
test duration 6 hours at 20 and 60°C. The concentration of the inhibitor in the test stream was 50-200 mg/l. The component composition of the inhibitor and the results of corrosion tests of the prepared samples are presented in the table of examples. 2-6). As can be seen from the above data, the individual components exhibit a low protective effect. The highest degree of protection of 50.9-55.3% is achieved only in the case of the use of monoethanolamine or distillation residue of MEA with their content in the flow of at least 200 mg/l. When the ratio of oil POD: nitrogen-containing component is below 1:1 (example 8), the protective effect is reduced, at - above 1.5:1 (example 11) does not increase more than 85%. With the optimal ratio of POD oil: nitrogen-containing component 1-2.5:1, a maximum protective effect of 87.8-100% is achieved at an inhibitor concentration of 50-200 mg/l (examples 7, 9, 10, 14, 15 and 16).
Examples 12 and 13 illustrate the improvement in performance characteristics (pour point and viscosity) with the introduction of SPFC and OP-7. Thus, it follows from the table that the components of the proposed formulation form a synergistic mixture, which makes it possible to significantly increase the effectiveness of protection in a mineralized coal-bearing stream, compared with inhibitory ability of individual components
ACID CORROSION INHIBITOR IN OILFIELD ENVIRONMENTS
An acid corrosion inhibitor in oilfield environments, including an oxygen-containing waste from the production of caprolactam and a nitrogen-containing organic additive, characterized in that, as an oxygen-containing production waste, it contains a distillation cube of the products of cyclohexane oxidation and dehydrogenation of cyclohexanol or its mixture with an alcohol fraction of caprolactam production, and as a nitrogen-containing additive - monoethanolamine or nitrogen-containing wastes from the production of ammonia or caprolactam at a mass ratio of oxygen- and nitrogen-containing components in a mixture of 2.5 - 1:1.
2. Inhibitor according to claim 1, characterized in that the distillation residue of monoethanolamine gas purification is used as nitrogen-containing ammonia production waste.
3. The inhibitor according to claim 1, characterized in that the distillation residue of caprolactam distillation is used as nitrogen-containing waste from caprolactam production.
4. The inhibitor according to claim 1, characterized in that the mass ratio of the components in the mixture of the distillation cube of the products of cyclohexane oxidation and dehydrogenation of cyclohexanol and the alcohol fraction of caprolactam production is 4: 1.
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Plasticizing and air-entraining additive for
building cement mortars and concretes. It is used as a component of cement mixtures to improve the technological performance of concretes and mortars in the construction of monolithic floors, ceilings, screeds, in the manufacture of complex and critical monolithic structures and products.
Any cement mixture, whether mortar or concrete, requires mixing it with water. The actual water demand of cement, i.e. amount of water
which he needs for hydration is about 15%.
However, there is one more necessary requirement - the mobility of the mortar / concrete mixture. With a water-cement ratio (W / C \u003d 15%), it will turn out to be
very rigid, practically “dry”: neither lay it, nor level it, moreover, do not pour it into the formwork.
In order for the cement mixture to become mobile, about 30% water is added to it (W/C=30%). When hardening such a mortar or concrete, part of the water is spent on the hydration of the cement, the rest - almost half -
evaporates or leaves through capillaries, leaving behind layers penetrated by communicating pores, causing additional concrete shrinkage and cracks.
This is especially critical for structures with large linear dimensions, such as concrete screeds in floor structures or monolithic foundations. Through these pores, water gradually penetrates into the thickness of the concrete / mortar and, when frozen, destroys the structure, corrosion of the reinforcement occurs.
To reduce excess water, plasticizers are added to cement mixtures during stirring. These additives, by thinning the concrete/mortar, make it movable and almost "self-leveling" with a minimum of excess moisture.
Therefore, no excess water remains in the thickness of the concrete/mortar to be removed. Communicating pores are not formed. Concrete acquires density, solidity, strength, its shrinkage is significantly reduced, crack resistance increases.
Such advantages have the ShchSPK plasticizer recommended for use in accordance with GOST 28013–89.
During mechanical mixing of the cement mixture, the SSPK contributes to the involvement of air microbubbles in the solution, which remain in it.
thicker in the form of closed spherical pores and further increase the crack resistance and bending strength of the structure.
SCHSPK increases the frost resistance of concrete by 1.5–2 times, reduces cement consumption by up to 8% while maintaining the required mobility and the specified
strength.
MODE OF APPLICATION
SCHSPK is added to mixing water or - with mechanical stirring - directly into the mixer. It must be taken into account: if you use SCHSPK, then to obtain the required mobility of the mixture, you will need water 20–30% less than usual. When used in plaster mortars, the best results are achieved in top coats by creating a dense, high-strength and water-resistant surface. If the concrete is being prepared or transported by an automixer, it is possible to add SHSPK directly to the mixer in the amount of one package, about 5 liters or more, at the discretion of the master.
CONSUMPTION RATES
The optimal rate of introduction of SCHSPK into concretes/mortars is 0.3–1.2% by weight of cement, i.e. approximately 100–300 g per 100 kg of concrete/mortar. About adding SCHSPK to the mixer - see the end of the previous paragraph.
STORAGE
Shelf life 1 year. Storage temperature is unlimited.
After thawing, the physico-chemical properties of schSPK are preserved. In case of slight delamination during storage, stir before use.
SECURITY MEASURES
SCHSPK non-flammable liquid. Has an alkaline reaction. According to GOST 12.1.007–76, it is forbidden to eat and smoke in places where the SCHSPK is used. In case of contact with exposed skin, rinse immediately with water.
PACKAGE
Plastic bottle 5.25 l; 70 pieces per pallet.
SCHSPK- alkaline effluent from caprolactam production, which is a waste from caprolactam production and is an aqueous solution of sodium salts of mono- and dicarboxylic acids, cyclohexanes and cyclohexanone. Brown liquid with moderate toxicity, density at 20 °C - 1.1-1.2 g/cm 3 , solution pH 10-13.
SCHSPK-m- modified alkaline effluent from caprolactam production, which is an aqueous solution of sodium salts of mono- and dicarboxylic acids, soda ash melt.
SPD-m- a product obtained on the basis of water-soluble high-boiling by-products of isoprene production. It is a light-moving, non-separating liquid from yellow to brown.
NChK- additive based on sodium or calcium salts of sulfonic acids, highly soluble in water. The liquid is dark brown in color, the density of a 10% aqueous solution is 1.023 g / cm 3, 30% - 1.063 g / cm 3.
KCHNR- aqueous solution of neutralized acid sludge. Dark brown liquid, highly soluble in water, density 1.049 g/cm 3 .
GKZH-10- transparent liquid from pale yellow to brown, miscible with water in all proportions, density 1.19-1.21 g/cm 3 .
GKZH-11- transparent liquid from pale yellow to brown, miscible with water in all proportions, density 1.19-1.21 g/cm 3 .
CHSS- a by-product of cellulose production, is a solution of a complex mixture of organic and inorganic substances. Contains sodium hydroxide, carbonate, sulfate, thiosulfate and sodium sulfide, lignin and its degradation products, sugars and hemicellulose decomposition products, sodium salts of resin and fatty acids.
M 1 - sodium salts of water-insoluble organic acids. Supplied as a pasty product with a solids content of at least 70% in metal or wooden barrels.
Air-entraining
FROM TO- saponified wood resin - a pasty product based on the sodium salt of abietic acid, obtained by saponification of heat-treated wood resin with alkali Low toxicity, fire and explosion safety. Release form - a plate in paper bags or a viscous product in barrels, transported by rail in covered wagons. It is stored under a canopy or indoors in kraft bags or barrels. Shelf life - 12 months.
START, START- neutralized air-entraining resin - additive based on sodium salts of abietic acid. Brown powder or monolith-lump, products are slowly soluble in water, low toxicity, low combustible. Supplied in bags, in wooden or steel barrels with a capacity of 50 to 250 liters. It is stored indoors, excluding product moisture. The storage period is unlimited.
The additive is introduced into the concrete mixture in the form of a 2.. .5% solution. The recommended dosage of the additive is 0.005 .. .0.05% by weight of cement. When used as part of complex modifiers, START (to avoid coagulation) is introduced separately from other additives.
The introduction of the additive contributes to an increase in the tensile strength of concrete, an increase in crack resistance, gas and water resistance.
KTP- a mixture of derivatives of resin and fatty acids formed during the extraction of tall oil from sulfate lignin. The solid product is brown in color, contains about 10% moisture. Let's well dissolve in water.
OTP- sodium salts of resin and fatty acids with a total alkalinity of 3-10%. Powder with a softening point of about 70°C.
OP- a pasty white product obtained by processing mono - and dialkylphenols with ethylene oxide, or an oily liquid from light yellow to light brown in color. Soluble in water.
With- sulfonol refers to foaming additives, the foam ratio is 10 for a 1% aqueous solution, the surface tension is 20.9 10 -3 N / m, it is used in monolithic concrete and reinforced concrete structures with high frost resistance, light porous concrete, building solutions. With- synthetic soap, a mixture of sodium salts of alkylbenzenesulfonates C n H 2 n + 1 C 6 H 4 SO 3 Na, where n \u003d 12, .. 18. White or light yellow powder, highly soluble in water. Non-toxic (irritates the upper respiratory tract). Release form - powder in bags or 45% solution. Supplied by rail in polyethylene or paper bags, in liquid form - in tanks.
Gas generating
GKZH-94- polymer of ethylhydrosiloxane, formed during the hydrolysis of ethyldichlorosilane. The content of active hydrogen is 1.3 - 1.42%. When using additives, the temperature of the concrete mixture should not exceed 30°C. Electric heating of concrete is not allowed.
GKZH-94M- the same, with the content of active hydrogen - 1.76%.
PGEN- transparent mobile liquid, insoluble in water, forms an emulsion. The kinematic viscosity of a 50% solution in toluene at 20 ° C is 1.6-2.2 s; it is not recommended for heat treatment of concrete.
136-41(GKZH-94) and 136-157(GKZH-94m)- organosilicon liquids (oil) polyhydrosiloxanes formed during the hydrolysis of ethyldichlorosilane are colorless or light yellow non-toxic, explosive, flammable, water-insoluble liquids with a guaranteed shelf life of up to 1 year from the date of manufacture at a temperature of 0 up to 20°С. Under atmospheric influence, liquids are able to polymerize over time, turning into a jelly-like irreversible product.
Additives based on polyhydrosiloxanes are used in the form of emulsions. The preparation of emulsions is a rather complicated process, therefore it is most reliable to use emulsions prepared directly by the manufacturer of the original product, because the manufacturer can choose the most effective stabilizer to obtain a stable emulsion. Silicon-organic emulsions may have different trade names for different manufacturers, the technical parameters are indicated in the product data sheet. Silicone fluids and emulsions based on them have a hydrophobic (water-repellent) property, reducing the wettability of the material with water. On the one hand, when hydrogen is released in an alkaline medium, additional cohesion of polysiloxane chains occurs. These neoplasms, insoluble in water and solutions of inorganic substances, are deposited in micropores and capillaries, to a certain extent hinder the penetration of aggressive liquids into them. On the other hand, the formed organometallic calcium siloxanes and silicon polymers of new chains with a trivalent bond between Si atoms, being chemically fixed on the surface of the cement stone, hydrophobize the walls of pores and capillaries due to the formation of a hydrophobic film. This increases the resistance of concrete in various environments, since the adhesion of salt and ice crystals to the hydrophobic surface of the pores is reduced. Such additives are indispensable for concretes with high requirements for frost and salt resistance, regardless of their composition and type of binder, including at low temperatures (up to minus 60°C); for structures operated in aggressive environments, sea water.
KE-30-04- GKZH-94 emulsion in water - a homogeneous white liquid is supplied in a 50% concentration in sealed containers with a capacity of 20.. .200 l with a guaranteed shelf life of 6 months from the date of manufacture at a positive temperature not higher than 20 ° C. It is transported by all means of transport, ensuring the safety of the container from mechanical damage, precipitation and direct sunlight.
The emulsion is introduced into the concrete mixture with mixing water diluted to 10 ... 25% or 50% concentration, depending on the capabilities of the dosing devices. The product is thoroughly mixed before use. Recommended dosages: GKZH-94-0.003... 0.1%, GKZH -94m -0.01... 0.07% by weight of cement in terms of 100% liquid. The effectiveness of additives increases with increasing mobility of the mixture and with the use of pozzolanic and slag Portland cement. The temperature of the prepared concrete mixture with additives should not exceed 30 ° C, therefore, electrical heating of concrete should be excluded.
PACK- aluminum powder, silvery fine powder, soluble in acids and alkali solutions, but insoluble in water and organic solvents, is an effective blowing agent for the production of aerated concrete. It is extremely flammable. The powder is packed in hermetically sealed metal cans with a capacity of 50 liters and stored in the manufacturer's packaging in dry enclosed spaces at a temperature not exceeding +35°C. They are transported by all types of covered transport with the installation of cans according to the principle of the densest packaging, which excludes their movement.
Powder is introduced into the concrete mixture in the form of a specially prepared paste (see "Guidelines for the manufacture and use of aluminum paste as a blowing agent for cellular concrete", M., NIIZhB, 1977). The calculated amount of aluminum paste with a surfactant is introduced into the concrete mix with mixing water. The recommended dosage is 0.005...0.01% by weight of the binder. The action of the additive is accompanied by the release of hydrogen. Overdose may reduce the strength of concrete. Cooking
1The method of alkaline-surfactant flooding of oil fields is considered. The peculiarity of this technology lies in the sequential injection of waste solutions from the woodworking (lignosulfonates) and petrochemical (alkaline runoff from caprolactam production) industries. From an economic point of view, the technology is resource-saving, since the cost of the ingredients used is significantly lower than those offered on the market for surfactants and alkaline components. For the effective application of this technology using new chemical reagents, a program of experimental and theoretical studies has been developed, which includes: field analysis, oil sampling, core sampling, laboratory studies, computer modeling and evaluation of the effectiveness of the technology used. The numerical values of the main parameters are determined: viscosity, oil saturation, oil acidity, permeability, water cut, temperature, clay content, formation water salinity, which guarantee the effectiveness of alkaline flooding with a high probability.
oil production
oil recovery factor (OR)
methods of enhanced oil recovery (EOR)
alkaline solution
surfactants
interfacial tension
acid number
oil displacement ratio
sedimentation
lignosulfonates (LSTA)
alkaline effluents from caprolactam production (SCHSPK)
1. Boxerman A.A., Mishchenko I.T. The potential of modern methods of enhanced oil recovery // Oil and Capital. "Technologies of fuel and energy complex". - 2006. - No. 6 (31). – P. 47–52.
2. Zheltov Yu.P. Development of oil fields. – M.: Nedra, 1986. – 332 p.
3. Foreign experience in the use of thermal, gas, chemical methods for enhanced oil recovery. – http://www.neftepro.ru/publ/25-1-0-57.
4. Lenchenkova L.E. Enhanced oil recovery of reservoirs by physical and chemical methods. – M.: Nedra, 1998. – 394 p.
5. Surguchev M.L. Secondary and tertiary methods of enhanced oil recovery - M.: Nedra, 1985. - 308 p.
6. Patent No. 2060375 of the Russian Federation / Gazizov A.Sh.; Klyshnikov S.V.; Galaktionova L.A.; Gazizov A.A. "Compositions for the displacement of oil from the reservoir". Published 05/20/96, Bull. No. 14.
7. Application of modern methods of enhanced oil recovery in Russia: it is important not to lose time // Ernst & Young. – 2013. – From 3–6.
Enhanced oil recovery is relevant both in the development of new fields and in the operation of old ones, even those that are significantly depleted. And in conditions when colossal oil reserves are concentrated in long-term developed fields, methods of enhanced oil recovery are of paramount importance.
At present, waterflooding of productive formations in order to intensify oil production and increase the oil recovery factor (ORF) is widely used in domestic and foreign practice. Waterflooding provides a high oil recovery factor due to two factors: maintaining reservoir pressure at an effective level for field development; physical replacement of oil with water in the pores of the reservoir. With all the advantages of the waterflooding method mastered by the oil industry, it nevertheless does not provide the necessary degree of oil recovery from the reservoirs. The main reason for the impossibility of achieving complete displacement of oil by water from reservoirs during their flooding is the immiscibility of the displaced and displacing fluids, as a result of which an interface is formed between these fluids and oil is retained in a porous medium by capillary forces. In addition, incomplete displacement of oil by water in the reservoir areas covered by flooding is due to the heterogeneous structure of the reservoir, hydrophobization of reservoir rocks due to the adsorption of heavy oil components on the surface of rock grains, as well as the difference in the properties of the displacing and displaced liquids, which leads to the appearance of hydrodynamic instability of the oil-water contact . As a result, there is a breakthrough of the displacing agent into production wells, a significant decrease in the coefficients of oil displacement from the porous medium and the coverage of reservoirs by drainage.
Oil remains in the porous medium of formations subjected to flooding in the form of films on rock grains and globules located in dead-end pores or in places of the porous medium of formations bypassed by water.
The use of chemical reagents during waterflooding can significantly increase the oil recovery factor. Injection of alkalis, aqueous solutions of surfactants (surfactants), acids and other reagents leads to a change in the properties of formation water and interfaces between water, oil and rock; to a decrease in the relative mobility parameter and an improvement in the oil-washing properties of water. For example, surfactants are used to modify wettability, can promote emulsion formation, carryover, bulk phase viscosity reduction and dispersion stabilization.
The mechanism of the process of oil displacement from the reservoirs by an aqueous low-concentration surfactant solution is based on the fact that in this case the surface tension between oil and water decreases from 35-45 to 7-8.5 mN/m and the wetting angle of the quartz plate increases from 18 to 27 g. Consequently, the wetting tension is reduced by 8-10 times. Studies by BashNIPIneft showed that the optimal mass concentration of nonionic surfactants in water should be considered 0.05-0.1%. Such a solution with interfacial tension at the oil-water contact of 7-8 mN / m, as studies show, cannot significantly reduce the residual oil saturation after conventional reservoir flooding, since the capillary forces, although reduced, are still large enough to keep the oil surrounded by water in large pores. Displacement of oil by an aqueous low-concentration surfactant solution at initial oil saturation and reduced interfacial tension leads to a slight decrease in the volume of oil blocked by water in large pores of the flooded part of the formation. Aqueous solutions of nonionic surfactants in this case increase the displacement efficiency by an average of 2.5-3%. The higher efficiency of oil displacement by an aqueous surfactant solution at initial oil saturation is explained by the fact that the reduced interfacial tension between oil and surfactant solution improves the mechanism of oil displacement from a microhomogeneous porous medium, but is not enough to move oil globules blocked in large pores by water. According to many researchers, aqueous solutions of surfactants with high interfacial tension (5-8 mN/m) are able to increase the final oil recovery of quartz weakly shale formations by no more than 2-5% compared to conventional flooding, if they need to be applied from the initial stage of development.
However, chemical flooding has its drawbacks. The biggest disadvantage of low concentration surfactant flooding is the high interfacial tension between the oil and the solution and the high adsorption of the chemical on the rock. He questions their use to increase the displacement capacity of water. The main disadvantage of polymer flooding is that the productivity of injection wells decreases sharply due to a sharp increase in apparent viscosity in the bottomhole zones, which cannot always be compensated by an increase in injection pressure due to the destruction of polymer molecules.
Using the method of alkaline flooding of oil reservoirs, which is based on the interaction of alkalis with reservoir oil and rock, it is possible to achieve a decrease in interfacial tension at the oil-alkali solution phase boundary and an increase in rock wettability by water.
When alkaline solutions come into contact with oils that interact especially actively with alkali due to low interfacial tension, finely dispersed emulsions of the “oil in water” type are formed, and with low-active oils - of the “water in oil” type.
Purpose of the study. The disadvantages of the alkaline flooding method are very strict criteria for its applicability in terms of oil activity. Mineralization of reservoir and injected water and a high content of clays in the rock can also exclude the possibility of applying the method.
In recent years, a combined waterflooding method, which is alkaline surfactant treatment, has begun to be used. The purpose of pumping such a combined composition during the implementation of the waterflooding process is to reduce the residual oil saturation of the reservoir being developed. This type of waterflooding combines the advantages of alkaline and non-ionic surfactant flooding and minimizes their disadvantages.
For the last twenty years, China has been the leader in the field of alkaline composition injection. This type of flooding has been successfully applied in major fields such as Daqing and Shengli. As a result, a 13% increase in oil recovery factor was obtained at the Daqing field, and 5% at the Shengli field.
Combined alkaline flooding has been used in more than 30 US fields. As a result of this type of impact, the average increase in oil recovery factor was 7.5%.
The main limiting factor in the application of this technology is the high cost of reagents. In this regard, there is a need to study the effectiveness of alkaline flooding using new cheaper components and compositions based on them. Lignosulfonates (LST) and alkaline effluent from caprolactam production (ACHSPK) in combination with a surfactant complex (ML-Super) were studied as such reagents.
Lignosulfonate (LST) is a natural water-soluble sulfonic derivative of lingin, they are formed during the sulfite method of wood delingification. Interest in lignosulfonates, both practical and theoretical, is due to their high surface activity.
Alkaline effluent from caprolactam production (ACS) is an aqueous solution of sodium salts of acid by-products of air oxidation of cyclohexane. ShchSPK is used in the construction industry and the building materials industry, as well as in oil production - to increase oil recovery.
Materials and methods of research
Injection of a solution of LST (anionic surfactants, with pH = 4-4.5), which are usually in a colloidal state in fresh water (hydration degree 30-35%), lowers the surface tension of water, creates stable emulsions and foams, and well suppresses adsorption centers Surfactant on the rock of the productive formation.
The injection of a solution of SCHSPK with ML-Super is also carried out on fresh water. When interacting with water, sedimentation occurs in highly permeable interlayers, their permeability decreases and, as a result, permeability heterogeneity is leveled with a simultaneous increase in the oil displacement coefficient by water with the formation of surfactants during the interaction of alkaline reagents with oil (pH = 11-13).
A feature of the proposed technology is the use of inexpensive waste from the woodworking and petrochemical industries. At the same time, it is supposed to develop a comprehensive waterflooding program that has both oil-washing and water-insulating properties, since the interaction of the two ingredients with each other and with saline formation water is accompanied by sedimentation.
It should be noted that the use of both the LST component and the SSPK component in enhanced oil recovery technologies has long been known in our country. So, in the patent of the Russian Federation 2060375 (priority 25.05.1994) as an alkaline additive to the injected water, it is proposed to use ASPK in concentrations from 4 to 99.9%. Gel-forming compositions based on lignosulfonates with various crosslinkers and additives are protected by copyright certificates back in the USSR - SU1716094 A1 (priority dated 05/21/1990). Nevertheless, these chemical reagents were not used jointly either in Russia or abroad.
The use of this technology using the proposed new chemical reagents should be justified by experimental studies. A program of such studies was developed, which includes: field analysis, oil sampling, core sampling, laboratory studies, computer modeling and evaluation of the effectiveness of the technology used.
Research results and discussion
Based on previous experience in the use of alkaline flooding, a number of criteria have been developed for selecting candidate fields for the successful implementation of alkaline flooding.
Criteria for selecting deposits - candidates for alkaline flooding
Thus, having analyzed the geological and physical characteristics of the deposit in accordance with these criteria, it is necessary to consider the technological parameters of the deposit. They must meet the requirements of alkaline flooding.
Oil sampling and core sampling is necessary to determine the geological and physical parameters of the field, as well as to confirm the effectiveness of the technology on composite models of the reservoir element of the field.
Laboratory studies consist in finding the acid number of oil (this parameter is one of the main criteria for the applicability of alkaline flooding), determining oil displacement factors and evaluating the increase in sweep efficiency on the simplest volumetric models.
The acidity of oil is the amount of alkali required to neutralize organic acids in 100 ml of oil, measured in mg.
The acid number is determined using the potentiometric titration method. The method consists in dissolving the tested oil product in an alcohol-benzene mixture and titrating the resulting solution with caustic potash. According to this criterion, oils are divided into highly active, active and low-active.
Displacement factors are determined on linear reservoir models.
The object of the test is the nature of the interaction of two immiscible liquids (oil and water) during their filtration under conditions corresponding (close) to reservoir conditions through a composite rock sample of regular geometric shape, prepared from the core of the studied reservoir and oriented parallel to the bedding.
Modeling of the process of oil displacement by water is carried out on a composite linear model of the formation element, assembled from 10 standard core samples taken from the productive formation of the field.
Formation water is used as a displacement fluid first, and then the proposed chemical reagents. Displacement is carried out at reservoir temperatures at a constant rate until the outgoing fluid is completely flooded.
At the end of the process of oil displacement by the working agent, the material balance method is used to calculate the displacement coefficients for the models of the reservoir elements of the field. The displacement coefficient changes in one direction or another, which allows us to speak about the effectiveness of this technology.
To evaluate the increase in sweep efficiency by flooding, a reservoir element model with parallel stream tubes is used. Streamtubes are composite models of a formation element, different in permeability by at least 5 times, having a common inlet and separate outlets. Through the flow tubes, oil is displaced by formation water, and then by the proposed reagents. At the same time, a change in volumetric velocities is recorded along parallel flow tubes, which indicates a redistribution of filtration flows and, as a result, an increase in the sweep factor.
The final step is to evaluate the effectiveness of the technology by calculating the flow rates before and after the implementation of the technology.
Conclusion
In this paper, alkaline-surfactant flooding is considered, the main limiting factor of which is the high cost of surfactant. In this regard, it was proposed to use cheaper reagents - woodworking waste (LST) and petrochemical (SCHSPK) industry. To evaluate the effectiveness of the proposed technology using new chemicals, a research program was developed, according to which each candidate field should be analyzed according to the developed selection criteria, after which, using laboratory studies and computer simulation, we can talk about the successful implementation of alkaline flooding.
Bibliographic link
Petrov I.V., Tyutyaev A.V., Dolzhikova I.S. DEVELOPMENT OF A PROGRAM FOR EXPERIMENTAL EVALUATION OF THE EFFICIENCY OF ALKALINE-SAS FLOODING FOR OIL FIELDS // Successes of modern natural science. - 2016. - No. 11-1. - S. 182-185;URL: http://natural-sciences.ru/ru/article/view?id=36207 (date of access: 07/24/2019). We bring to your attention the journals published by the publishing house "Academy of Natural History"
