Method for the production of carbon-mineral adsorbent

 

(57) Abstract:

The invention relates to a process for the production of adsorbents for the purification and disposal of sewage and natural waters contaminated with organic substances, and can be used in environmental technologies in different industries. Mix 1 wt.h. spent clay-containing drilling fluid and 0,06-0,25.h. grass meal (crushed vegetable waste grain breads and grain-legumes) and thermoablative at 850-900oC for 0.3 to 0.4 hours Method provides receiving of the adsorbent increased strength and increases its adsorption capacity when cleaning liquids from petroleum products and synthetic surfactants when the content below and above the critical concentration of micelle formation. 1 C.p. f-crystals, 1 table.

The invention relates to a process for the production of adsorbents for the purification and waste of natural waters contaminated with organic substances, and can be used in environmental technologies in different industries.

Analysis of the existing state of the art showed the following:

- known method for the production of carbon-mineral adsorbent, comprising mixing Dre the organic polyalcohol in the appropriate quantity and heat treatment in two stages, moreover, the first conducting isothermal exposure at 120 - 150oC for 2 to 3 hours, the second pyrolysis at 450 - 600oC in non-oxidizing atmosphere for 1 to 2 h (see and.with. N 1790996 from 15.02.91, CL 01 J 20/00, publ. in ABOUT N 4, 93, a).

The disadvantage of this method is the low mechanical strength of the adsorbent, low sorption capacity when cleaning liquids from petroleum products and synthetic surfactants (detergents).

The strength of the adsorbent by this method is slightly higher than the mechanical strength of wood activated carbon, because the organic compounds included in the composition of the adsorbent, at 450 - 600oC carbonitride and solid crystalline framework within which the strength of the adsorbent, is missing. Small adsorption capacity of the sorbent due to the relatively small pore volume (0.95 cm3/g and below);

as the prototype was taken way to obtain carbon-mineral adsorbent, comprising heat treatment of compounds containing aluminum oxide - cake of the wastewater treatment process of the production of a copolymer of Acrylonitrile, butadiene, styrene, containing aluminium hydroxide, the copolymer of Acrylonitrile, butadiene and stelena), moreover, the heat treatment is carried out at 700 - 800oC (see and.with. N 1274762 from 05.04.84, CL 01 J 20/08, 20/20, publ. in ABOUT N 45, 86 g).

The disadvantage of this method is the low mechanical strength of the adsorbent, low sorption capacity when cleaning liquids from petroleum products and detergents.

The heat treatment of the oxide at 700 - 800oC does not allow the adsorbent with high mechanical characteristics, because at these temperatures occurs dehydration of chemically bound water, which is accompanied by the destruction of the crystal lattice of the material. For the formation of anhydrous aluminosilicate of Melita, which improves the physical and mechanical properties of the adsorbent, temperature 800oWith not enough. Therefore, the mechanical strength of the adsorbent small. The liquid particles of the adsorbent are square or circular in shape (length, width and thickness are approximately similar in magnitude). Further, when the heat treatment in the adsorbent are formed in a large number of dead-end (round) pores. They practically do not participate in the adsorption process and are a kind of "dead zones" in the porous structure of the adsorbent. The result is a significant part of the micro - and mesopores of lechaeum long but this process is mainly due to the increase in macropores, which does not substantially have a positive impact on the adsorption capacity of the adsorbent. At the same time decreases its mechanical strength. In addition, in the charge no water-soluble organic compounds (carboxymethylcellulose, lignosulfonates, and so on), which during the heat treatment are the main sources of formation of micro - and mesopores. The latter is also one of the reasons for the low adsorption capacity with respect to high-molecular organic pollutants, as well as detergents, especially at concentrations above the critical micellization concentration (CMC), when the molecule surfactants form aggregates (micelles) of several molecules.

The technical result that can be obtained by carrying out the present invention, is as follows:

- increases the strength of the adsorbent and increases its adsorption capacity when cleaning liquids (sewage, natural waters from oil and surfactants, when the content below and above the CMC.

Technical result is achieved by using a known method of producing carbon-mineral adsorbent, zaklyuchayushchiesya substances and fillers in the form of carbon-containing flour with subsequent thermal treatment, where as industrial waste use waste clay-containing drilling fluid (AGBR), and the carbonaceous flour - herbal flour in the ratio of wt.h., 1:0,06 - 0,25 respectively, and perform heat treatment at 850 - 900oC for 0.3 to 0.4 hours. As grass flour, you can use shredded vegetable waste grain breads and grain-legume crops. To grain loaves are: wheat, rye, barley, oats, maize, millet, sorghum, rice, buckwheat, grain legumes crops include peas, soya, lupins, beans, broad beans, rank, chickpeas, lentils (see classification, see the book. P. p. Vavilov, in. A. Gritsenko, V. S. Kuznetsov Workshop on crop production. M.: Kolos, 1983, S. 5, 48).

AGBR is a waste drilling process and represents a complex physico-chemical system based on inorganic (mineral) compounds (for example, on the basis of aluminum compounds clay bentonite and barite, chalk, and so on) and high-molecular organic substances (for example, carboxymethylcellulose (CMC), ogledaloto reagent (USR), condensed sulfite-alcohol bard (kssb), etc.

AGBR may contain the following components, wt%:
logical properties, filtration and stabilization (e.g., CMC, USR, kssb) - 1,0 - 15,0

PH regulators (for example, hydroxides of sodium, calcium, sodium carbonate) - 0,01 - 2,0

Lubricating additives (e.g., oil, graphite, oil and waste production) is 0.1 to 15.0

The chlorides of sodium, calcium, magnesium and 0.1 to 20.0

Water - the rest

The chemical composition OGBR the following, wt.%

SiO2- 25 - 31

Al2O3- 18,5 - 20,5

CaO - 1,8 - 3,8

MgO - 1,1 - 2,6

Fe2O3- 4,1 - 5,2

BaSO4- 5,0 - 30,0

Na2O+K2O - 2,5 - 3,2

SPT - 9 - 15

The dispersed composition comprises mineral component with a particle size of generally not more than 20 μm. Coarse particles are practically absent, as they are quickly deposited under the action of Stokowski forces. Suspended solids are represented by clay, the particles of the filler and drilling, as well as high-molecular compounds and insoluble mineral salts. Crude oil and petroleum products contained in AGBR in film, emulsified state. Dissolved impurities is represented mainly by mineral salts. Analysis AGBR different areas of the drilling showed that the composition and properties AGBR change in the following range: pH 7,5 - 10,0; weighted prophetic">

GOSTs, OSTs, on THE process fluid in the drilling process and AGBR missing. Due to the variety of geological conditions of the wiring holes on the production, as a rule, a standard of the enterprise, for example, on the particular composition of the drilling mud etc., Composition and properties AGBR listed in various sources:

1. AOI Series "Corrosion and protection in the oil and gas industry". Bykov, I. Y. environmental Protection during construction of the wells. Vol. 1 (45), M, 1985, S. 16:

pH 8,8; biological demand for oxygen (BOD) - 776,8 mg O2/l; oil - 712 mg/l; suspended solids - 9983,3 mg/l

2. AOI Series "corrosion control and protection of the environment". Closed system water drilling. Vol. 1 (88), M, 1989, S. 5 - 6:

pH 8 to 10, the total mineralization of 4 - 9 g/l, BB - 8 - 42 g/l, oil - 0.2 to 1.0 g/l, MIC - 2,8 - 3,8 g O2/l

3. AOI Series "corrosion control and protection of the environment". Shemetov C. Y. Purification of drilling wastewater by electrocoagulation. M., 1989, S. 5 - 8:

pH 7,5 - 9,0, BB - 3,0 - 5,0 g/l, oil - 0.1 - 0.3 g/l, COD of-1.0 and 1.75 g/l

Herbal flour is used according to GOST 18691-88 "Feed herbal artificially dried. Technical conditions". Herbal flour prepared from mn is the size less than 3 mm Other indicators (carotene content, ash, protein and crude fiber) grass meal 1, 2 and 3 classes are not strictly regulated, because when using it as a filler to obtain organic-mineral adsorbent, the above figures do not play a significant role. It is considered preferable to use as filler herbal flour obtained by grinding agricultural vegetable waste remaining after the harvest of cereals and pulses. Moreover, to obtain herbal flour from waste some plants (sunflower, corn, sorghum) is necessary before grinding mills further subjected to grinding to obtain a cut with dimensions of 100 mm

Known: the use of the spent solution, pre-neutralized phosphoric acid, nitric acid, or their mixture to pH 6 - 8 water dispersion improver to improve reclaiming efficiency by increasing the content of water-stable aggregates (see and.with. N 1330145 from 18.04.85, class C 09 K 17/00, publ. in ABOUT N 30, 87, a); application of the extract, not containing chromium compounds, mud as amendment of acid soils (see and.with. N Cai with thin clay in the raw mix for bricks to improve crack resistance during drying and lower temperature firing and cost (see A. with. N 1655947 from 03.05.88, class C 04 B 33/00, publ. in ABOUT N 22, 91 g); use of waste drilling mud without chromium compounds in the mixture of seeds of perennial grasses, physiologically acid fertilizers and water in compositions for strengthening of earthworks to improve the effectiveness of the strengthening of slopes by accelerating the formation of vegetation cover (see and.with. N 1587137 from 10.10.88, CL E 02 D 17/20, publ. in ABOUT N 31, 90 g).

Know the use of bacteriophages herbal flour mixed with purified alumina, fine peat and ammonium nitrate to increase the degree of purification in the way of cleaning water from pesticides (see and.with. N 912661 from 01.04.80, class C 02 F 1/28, publ. in ABOUT N 10, 82 g).

Thus, no correlation methods or compositions based on the use of AGBR mixed with herbal flour in the claimed proportions of components with subsequent thermal treatment and achievable technical result.

The inventive method involves an inventive step.

The mineral part of the adsorbent is represented mainly bentonitovykh clays of the montmorillonite type, as well as drilled rock, consisting of quartz, carbonates, gypsum, is such a body, resistant to mechanical, physical and chemical effects. When the firing temperature to 800oC dehydration takes place, i.e. the removal of chemically bound water, the crystal lattice of the material is destroyed and the mass loses its plastic properties. In this period there is a firing shrinkage of the mass and the reduction of its mechanical strength. The material gets the greatest porosity. In the temperature range 850oC - 900oC alumina Al2O3and silica SiO2connected in anhydrous aluminosilicate - mulit significantly improve the physical and mechanical properties of the adsorbent. With increasing firing temperatures above 900oC begins to form liquid phase resulting residual deformation products and a reduction in porosity of the adsorbent.

To avoid this, the rise of temperature during firing of the sorbent is terminated at a temperature not exceeding 900oC, i.e. at the stage, providing the appearance of a minimum necessary amount of the liquid phase for the formation of adhesions (links) between the dehydrated particles pineoblastoma materials, decarbonisation particles of carbonates and quartz grains. This creates conditions for a sufficient IU the moisture, then, when the temperature of 170-270oC starts the release of gases (mainly CO and CO2and vapours of organic acids, alcohols, aldehydes and other compounds. At a temperature of 400oC ends distillation of volatile substances, the output of which can be up to 70% by weight of organic compounds contained in the charge. Due to the difficult access of the oxidant (oxygen) organic component of the mixture the processes occurring during the heat treatment similar to the processes taking place during pyrolysis. After removal of the mass of moisture, vapors of organic compounds and volatile substances formed porosity of the adsorbent.

Abgar organic compounds contained in AGBR and the filler leads to the fact that on the surface, then a layer of activated carbon, thereby increasing the adsorption capacity of the adsorbent. In addition, as a result of carbonization and activation on the surface of pores are formed uncompensated positive electric charges. Therefore, when the contact of the adsorbent with polluting substances that have a negative charge, is not only molecular adsorption, but also pronounced adhesion due to electrical forces. In addition, organise coal, but partially burn out, forming pores, the size of which is comparable to the size of the molecules of hydrocarbons, soluble, colloidal, and insoluble in water natural and synthetic high molecular compounds that promotes their active sorption.

The firing temperature should not be brought to the sintering of the ceramic material (stage silicotuberculosis), since in this case there is a reduction of total porosity and especially the volume of micropores.

The heat treatment time is 0.3 to 0.4 hours is optimal when the degree of intoxication of organic compounds in the mixture is 50 to 70%, the content of micro - and mesopores is sufficient to obtain the maximum sorption capacity for petroleum products and detergents in their content in the purified water below and above the CMC.

Increasing firing temperatures above 900oC and more than 0.4 hours leads to an increase in the degree of intoxication (>70%) of the organic portion of the mixture and consequently decreases the adsorption capacity of the sorbent. The firing temperature of the mixture less than 850oC and less than 0.3 hours leads to a decrease of mechanical strength of the sorbent and the decrease in the volume of micropores in the result is not complete carbonization of organic compounds, WMO 870oC, I get the organic adsorbent with low total pore volume, which affects the adsorption capacity of both petroleum products and detergents. This is due to the small amount of activated carbon produced in obare organic substances.

If 1 wt.h. AGBR to take more than 0,25.h. herbal flour and make a firing charge at 870oC, I get the organic adsorbent with a high total pore volume, but with a relatively low content of meso - and micropores, as well as, equally importantly, with reduced mechanical strength.

In more detail the essence of the invention is described in the following examples.

Example 1.

A mixture consisting of 1 wt.h. (400 g) AGBR and 0.25 wt.h. (100 g) grass meal (corn straw) thermoablative in a muffle furnace at a temperature of 850oC for 0.30 hour (18 minutes). The resulting cake crushed in a ball mill, sieved through a sieve and selected fraction of 0.5 - 1.0 mm, the resulting adsorbent has the following characteristics: adsorption capacity for phenol 273 mg/g, oil 310 mg/g, detergents 135 mg/g, the mechanical strength of 87%, the total pore volume of 2.33 cm3/,

The adsorbent in the number of the column before loading of the adsorbent is placed a layer of glass wool height 20 - 30 mm To eliminate "wall effect" after every 100 mm column is placed an elastic rubber ring with an external diameter of 50 mm as treated water use industrial Krasnodar UGS, pre-cleaned of sediment and suspended solids by filtration through the filtration load of quartz sand. Filtering the wastewater through adsorption column is carried out in the downward direction with a constant velocity equal to 1.5 m/h. Waste water is filtered through the adsorption column during the 2 hour and 15 minutes After treatment the concentration of oil products is 23 mg/l, detergents (below CMC) 20 mg/l, the degree of purification from oil products to 94.5%, detergents (below CMC) of 92.6%.

Example 2.

A mixture consisting of wt.h. (400 g) AGBR and 0.06 wt.h. (24 g) grass flour (wheat straw) thermoablative in a muffle furnace at 870oC for 0.35 hours (21 min) and then conduct all operations as described in example 1. The resulting adsorbent has the following characteristics: adsorption capacity for phenol 247 mg/g, oil 287 mg/g, detergents 129 mg/g, the mechanical strength of 96%, the total pore volume 2,31 cm3/year Waste water is filtered through the adsorption column. After treatment, the concentration of the nave is 9%.

Example 3.

A mixture consisting of 1 wt.h. (400 g) AGBR and 0.1 wt.h. (40 g) grass meal (peas, straw) thermoablative in a muffle furnace at 900oC for 0.40 hour (24 minutes) and then conduct all operations as described in example 1. The resulting adsorbent has the following characteristics: adsorption capacity for phenol 335 mg/g, oil 410 mg/g, detergents 200 mg/g, the mechanical strength of 96%, the total pore volume of 2.26 cm3/year Waste water is filtered through the adsorption column. After processing petroleum concentration is 5 mg/l, detergents (below CMC) 8 mg/l, the degree of purification from oil products 98,8%, detergents (below CMC) 97,0%.

Splitting and crushing of raw materials for herbal flour is carried out in the unit IR-3 with a cutting knife drum. The humidity of the raw material should be no more than 30%. The length of the particle mass from 2 to 100 mm, Herbal powder made from the crushed mass is prepared in hammer mills type AVM (AVM - 0,65; AVM - 1.5 a; AVM - 3.0) or universal mill MDU - 04. The particle size of the grinding govern the changing of sieves with apertures 2; 3; 4; 5; and 7 mm

Forming a mixture of AGBR and herbal flour is used to make plastic method with humidity weight 15 - 25% in screw or worm p is th, as a rule, amounts to about 10 wt.%.

The firing of the charge is carried out in a tunnel furnace where the mixture screw mixer is fed to the conveyor. Heat treatment of the charge produced by an open fire using gas burners.

Carbon-mineral adsorbent will be used in the preparation of wastewater prior to disposal in deep aquifers. Wastewater generated at the stations of underground gas storage (UGS) before being pumped through the main bore in the absorbing layers should be cleaned from mechanical impurities, oil and other organic compounds that pollute the water. Without purification of the injected wastewater quickly collateral (pollute) the bottomhole formation zone in the injection well. The well productivity falls, there is a need to stop it, the repairs to restore the permeability of the absorbing layer, and in some cases, and drilling a new well.

Treatment of waste water adsorption on the proposed carbon-mineral adsorbent carried out on the last stage of preparation of the water before pumping it into the reservoir using both standard and non-standard borolouorca, the sump and clarifier, where purified from suspended, emulsified, and solid particles.

Then the water in the piping system goes down in the adsorber filled with carbon-mineral sorbents. At the bottom of the adsorber install a metal grid on which the load block or anthracite with a diameter of grains 3 to 5 mm, the thickness of the supporting layer 10 to 50 mm, the size of the adsorber determined on the basis of his performance, water velocity and length of the mass transfer zone. As adsorber can be used separators volume of 4 m3with a working pressure of 0.6 MPa used for UGS for the purification of gas from liquid in field gas treatment units. The number of installed adsorbers three: two in operation and one in reserve. For pumping wastewater and water emulsions are widely used centrifugal type pumps CR-150-150, CN-170-190 and other high performance are available as modular pumping stations. The motors for these pumps are used type wise-800-1500 kW and ASP-800-1250-1600 kW.

You can also use oil mud pumps used in the drilling of wells, for example, pumps brand NGR.

In some cases, pridratsya into the reservoir under hydrostatic pressure.

Regeneration of the adsorbent is carried out with steam from the boiler to UGS or mobile steam units that are used in the processes of drilling and repair of wells, cleaning and gas transportation and other technological operations.

In comparison with analogues of the advantages of the proposed carbon-mineral adsorbent is as follows:

- adsorption capacity for phenol increases of 1.1 - 1.5 times (from the prototype), which increases the cleaning efficiency of detergents when their concentration in the treated water of less than or more cash registers;

parameters of mechanical strength increase 1.1 - 1.3 times (from analog), which significantly improves technical characteristics of the adsorbent increases the operation time and the number of regeneration cycles of the adsorbent (relatively prototype quantitative data on the mechanical strength are not available, therefore we are only theoretical considerations on the issue);

- expanding the raw material base for the production of adsorbent;

- utilized unused at present toxic drilling waste (AGBR) and hard-acquirable low-calorie agricultural wastes;

- solved the most important social problem kanyirninpa adsorbent, which consists in mixing the industrial waste on the basis of inorganic aluminum compounds, high-molecular organic substances and fillers in the form of carbon-containing flour with subsequent heat treatment, characterized in that as an industrial waste on the basis of inorganic aluminum compounds and high-molecular organic substances use exhaust clay-containing drilling mud, and the carbonaceous flour - herbal flour ratio, wt.h., equal to 1:0,06 - 0,25 respectively, and perform heat treatment at 850-900oC for 0.3 to 0.4 PM

2. The method according to p. 1, characterized in that as herbal use flour milled vegetable waste grain breads and grain-legume crops.

 

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