METHOD OF TREATMENT OF CONTAMINATED WATER BY MEANS OF ADSORPTION AND NANOFILTRATION

AREA OF TECHNOLOGY, WHICH INCLUDES THE INVENTION

The present invention relates down the method of treating the contaminated water.

It is more concrete specific, the present invention relates down the method of the water treatment, contaminated by polar and/or nonpolar organic compounds and/or by salts of heavy metals and/or by the oil, dispersed or before the emulsion, that includes the stage, before which they direct contaminated the water beside the system indicated, which contains, at least, one adsorptive block and, at least, one nano-filtrational block.

PREVIOUS TECHNOLOGICAL LEVEL

Industrial effluents, which must be processed before they will be released or used repeatedly, include the contaminated waters, which contain polar and/or nonpolar organic compounds and/or salts of heavy metals and/or the oil, dispersed or before the emulsion. The waters indicated can come from many branches of industry, such as, for example, aluminum and steel industry, chemical and/or petrochemical industry, auto industry, petroleum industry.

In particular before the petroleum industry and in the course of output, and in the course of petroleum refining the large number of contaminated water is formed. For example, in the course of output this and the following water, extracted together with the oil, and the forced water, obtained based on the recovery of water down the surface together with the hydrocarbons, shaken beside the bore hole for maintaining the values of pressure against the appropriate levels.

The typical contaminiating connections, which are present before the effluents, obtained based on the petroleum industry, in particular, before the following water and the effluents of oil refineries (for example, the cooling water, wash water, ground water of oil refineries) and effluents of those obtained based on the petrochemical industry (for example, the cooling water, wash water, ground water petrochemical enterprises), are represented before Table 1.

Table 1 class of the contaminiating connections examples of the contaminiating connections polar and nonpolar organic compounds aliphatic hydrocarbons, carboxylic acids, it is not necessary, the halogenated phenols, is not necessary, the halogenated aromatic connections, glycols, alcohols, ethers (methyltertbutyl ether, ethyltertbutyl ether), aldehydes, ketones, halogenated solvents oil dispersed or beside this hydrocarbons, alkyl phenols the dissolved minerals of salt, which contain Na+,+,2+,2+,2+, Sr2+, Fe2+ as the cations and Cl”, SC>42~,2~,~ as the anions of salt of the heavy metals, such as Cd, cg, SI, Pb,, Ni, Ada, Zn natural radioactive materials chemical additives the inhibitors of corrosion and formation to scale deposit, biocides, emulsifiers, antifoam agents the weighed solid particles lime attack, paraffins, microorganisms, asphaltenes, the oxides of iron the dissolved gases the dioxide of carbon, oxygen, hydrogen sulfide working for the removal of the above-indicated contaminiating connections is known before the technological level. Examples of the types of the working indicated are given before Table 2.

Table 2 types of working examples of working physical adsorption on activated carbon (GAC), zeolites, resins; precipitation by dissolved air; centrifugation;; evaporation; the filtration through the sandy layer; electrodialysis;/evaporation; diaphragm cleaning (MF, UF, NF, R0)

Chemical is precipitation, oxidation, electrochemical methods, photocatalytic methods, the method Of, ozonization, action by ionic liquids at room temperature; emulsification biological aerobic methods, anaerobic methods mentioned above physical and/or chemical treatment, as a rule, conduct on the sea platforms, where the space limited can be used compact technologies.

However, to the workings indicated, besides the high cost, can be characteristic some deficiencies. Actually, the workings indicated are not always completely effective with respect to of removal and above-indicated polar or nonpolar organic compounds, and above-indicated dissolved minerals, or mentioned above oil, dispersed or before the emulsion.

Based on the other side, indicated above biological workings, as a rule, are accomplished beyond coast installations. However, biological the workings indicated, generally, cheaper and more effective in comparison with those indicated higher than the physical and/or chemical treatment, not always can be used, in particular, before the presence:

salts before the high concentration, the strongly inhibiting activity utilized microorganisms; - the substances, toxic for the biomass (for example, benzene); - the organic matter, which are difficultly yielded to (for example, methyltertbutyl ether).

Furthermore, biological the workings indicated require control besides the large volumes of the sediment produced.

Finally, additional problems can be the consequence of the second pollution as a result of the use of the chemical additives, which use for control besides the methods of the above-indicated chemical, physical and/or biological working.

Before the technological level is described working the contaminated water with the use of microcellular alumosilicates, i.e., zeolites.

For example, before the patent application of USA 2004/0206705 is described the method of the water treatment, contaminated as far as nonpolar compounds, that is characterized by the fact that is conducted working the contaminated ground water, which is consisted before the passage of the water concerning the permeable reactive barrier (PRB), placed on the spot perpendicular down the flow of ground water, in this case, reactive means consists of one or several nonpolar zeolites, which have relationship the oxide of silicon/the oxide of aluminum more than 50 and having the structural channels (i.e., time), whose size is analogous down the molecular dimension of the contaminiating compounds. It is asserted that the method indicated is suitable for the effective and selective removal of the nonpolar contaminiating compounds in comparison with by the mineral salts, usually dissolved before the water.

Before the patent of USA 7341665 is described the method of the water treatment, contaminated as far as nonpolar organic compounds and/or by heavy metals, which consists before the circulation of the water through the system, which contains, at least, two types of zeolites, which have relationship the oxide of silicon/the oxide of aluminum more than 50 and placed before the sequence, in this case, first zeolite, through which they pass water, it differs regarding the high adsorptivity and the presence in structural channels (i.e., times) with size from 7[A] to 50[A], and second zeolite it is characterized by the high ability of the removal of the molecules, whose diameter is compared with the size of structural channels (i.e., times), which are been located in the range from 5[A] to 7[A]. It is asserted that method described above is suitable for the effective removal of the nonpolar contaminiating organic compounds and if they are present before a small quantity, and if they are present in large quantities because of the synergistic effect of two zeolites.

Before the technological level working the contaminated water with the use of the membranes is also known.

For example, Visvanathan and other in article “Volume of reduction of of produced of water of generated of from of natural of GaS of production of using of membrane of technology” (decrease of the volume of following water during the output of natural gas with the use of diaphragm technology), published beside “Water Of science and Technology” (2000), Vol.

41, pp. 117-123, describes the method of treating the following water of the formable before the method output of natural gas, the containing stage of the direction following of the water beside the block of preliminary working indicated, which contains the membrane (UF) or the nano-filtrational membrane (NF), obtaining and; the direction of obtained before the block of preliminary working beside the block of working, which contains the membrane (RO). It is asserted that preliminary the working indicated is required for averting the pollution of membrane.

Mondal and other in article “Produced of water of treatment by of nanofiltration and reverse of osmosis of membranes” (working the obtained water with the aid of the nano-filtrational and membranes), published beside “Journal of Of membrane Of science” (2008), Vol. 322, pp. 162-170, describe working the following water, manufactured before the method of output with oil or gas, with the aid of the nano-filtrational and membranes. In particular, the following membranes were tested:

- NF 270: thin-film composition membrane on the basis of piperazine and polyamide (nano-filtrational); - NF 90: thin-film composition membrane on the basis of aromatic polyamide (nano-filtrational); - BW 30: thin-film composition membrane on the basis of aromatic polyamide ([obratnoosmoticheskaya]).

Tests demonstrated the pollution of the membranes. On the membrane BW 30 is obtained of the best quality in comparison with the nano-filtrational membranes NF 270 and NF

Ahmadun and other before the survey “Review of of technologies of for of oil and GaS of produced of water of treatment” (survey of the technologies of working as far as that obtained simultaneously with oil and gas of water), published beside “Journal of Of hazardous Of materials” (2009), Vol. 170, pp. 530-551, describe several technologies of working the following water, extracted before the petroleum and gas extracting industry. Among them are described, for example, the technologies of working by means of the micro-filtrational membranes, the membranes, the nano-filtrational membranes and the membranes.

Before the patent of USA 5028336 is described the method of water treatment (for example, the following water, extracted with oil production or gas), which has the low pH and which contains the water-soluble dissolved organic electrolytes, which includes stages on which: increase the pH of the water indicated so as to obtain the alkalized water, which contains the water-soluble dissolved organic electrolytes; subject nano-filtration alkalized the water indicated, which contains the water-soluble dissolved organic electrolytes with obtaining (i) of aqueous, which contains the water-soluble dissolved organic electrolytes before the higher concentration, and (11) aqueous, which contains the water-soluble dissolved organic electrolytes before the lower concentration; is separated aqueous indicated, which contains the water-soluble dissolved organic electrolytes before the higher concentration; and is separated aqueous indicated, which contains the water-soluble dissolved organic electrolytes before the lower concentration.

It is asserted that working described above is suitable for the effective removal of the water-soluble dissolved organic electrolytes, which are present before the water indicated.

However, the methods represented above can demonstrate some deficiencies. Actually, the above-indicated methods are not always capable of providing reaching the required results.

Based on one side, the methods, before which are used microcellular alumosilicates (for example, zeolites), do not ensure the effective removal of polar organic compounds with the small number of carbon atoms (for example, with the number of carbon atoms are less or equal 8), in particular, in the case of the oxygen-containing polar organic compounds, such as alcohols, glycols, aldehydes, ketones and carboxylic acids. Furthermore, the use microcellular of alumosilicates indicated does not make it possible by effective means to move away salts of heavy metals and oil, dispersed or before the emulsion.

Based on the other side, the methods with the use of the membranes do not always make it possible by effective means to move away the nonpolar organic compounds, such as, for example, benzene, ethylbenzene, toluene, xylenes (known as), aggressive with respect to the membranes indicated. In particular, with the high concentration of the connections (for example, concentration, more or the equal to 10 parts down million) indicated can occur the depolymerization of the membranes and, thus, making for the sake of their impossible for the use about the designation.

Thus, before the applicant arose the problem of finding the method of the water treatment, contaminated by polar and/or nonpolar organic compounds and/or by salts of heavy metals and/or by the oil, dispersed either before the emulsion, suitable for the effective removal and organic compounds for the sake of the small and large number of carbon atoms, and salts of heavy metals, and also oil, dispersed or before the emulsion.

Applicant discovered, that via subjection to working contaminated the water indicated, which contains the direction contaminated of the water beside the system indicated, which contains, at least, one adsorptive block, which contains, at least, one microcellular or alumosilicate, and, at least, one nano-filtrational block, which contains, at least, one hydrophilic nano-filtrational membrane, which has distinguishing features, possible by effective means to move away polar and/or nonpolar organic the compounds indicated, and the salts of heavy metals indicated, and also the indicated oil, dispersed or before the emulsion, preventing the above-indicated problems of the depolymerization of the membrane. In particular, working with the aid of microcellular or alumosilicates indicated makes it possible to move away polar organic compounds with the number of carbon atoms of more than 8, and the nonpolar organic compounds, which are present before contaminated the water indicated both before the small, and high concentration (for example, in the concentration from 1 part down million to 30000 parts down million), whereas working as far as nano-filtration makes possible to remove polar organic compounds with the number of carbon atoms less or at the point of the equal to 8, in particular, oxygen-containing organic compounds, such as alcohols, glycols, aldehydes, ketones and the carboxylic acids, which are present before contaminated the water indicated both before the low and before the high concentrations (for example, in the concentration from 1 part down million to 30000 parts down million). Furthermore, working with the aid of microcellular or alumosilicates indicated makes it possible to avoid the pollution of hydrophilic nano-filtrational membrane and to, therefore, increase the period of service and realization by the membrane of its functions and to save time and money. Furthermore, working with the aid of microcellular or alumosilicates indicated makes it possible by effective means to move away the oil, dispersed or before the emulsion. Furthermore, nano-filtrational the working indicated makes it possible to move away salts of heavy metals.

The above-indicated working guarantees the high quality of the completely purified effluents. Actually, the water, obtained of at the end indicated working, corresponds to the levels of the removal of polar and/or nonpolar organic compounds, determined as far as normative limits, according to legislative directive 152/2006, and it does not need any additional working.

By the task of present invention is, therefore, the method of the water treatment, contaminated polar and/or nonpolar organic compounds and/or by salts of heavy metals and/or by the oil, dispersed or beside the emulsion, the including stage of the direction contaminated of the water beside the system indicated, which contains:

- at least, one adsorptive block, which contains, at least, one microcellular or alumosilicate; at least, one nano-filtrational block, which contains, at least, one hydrophilic nano-filtrational membrane; in this case, hydrophilic nano-filtrational the membrane indicated has with the water contact angle, is less or equal to 45°, preferably, located in the range from 25° to 40°.

“Contact the angle indicated” was measured, as is described Greens and other in the article “Polymeric of nanofiltration of of binary of water-alcohol of mixtures: Influence of of feed of composition and membrane of properties on of permeability of ans of rejection” (polymeric nano-filtration of the binary water-methane mixtures: Influence of the composition of raw material and properties of the membrane beyond the permeability and the detainment), published beside “Journal of Of membrane of science” (2005), Vol.

255, pp. 255-264.

For purposes of present description and accompanying formula of invention, determination of numerical intervals the outer limits always contain, if another is not indicated.

For purposes of present description and accompanying formula of invention, term “adsorptive block” indicates the undertaken as a whole device, required for the realization of adsorption and usually which contains, at least, one feeding capacity, at least, one delivery pump, at least, one adsorptive column, which contains, at least, one microcellular or alumosilicate, at least, one detector for the tracking of the general content of organic carbon. Additional details with respect to adsorptive the block indicated are given below (utilized materials and methods).

For purposes of present description and accompanying formula of invention, term “nano-filtrational block” indicates the undertaken as a whole device, necessary for the realization of nano-filtration and usually which includes, at least, one feeding capacity, at least, one delivery pump, at least, one nano-filtrational reservoir, before which there is, at least, one hydrophilic nano-filtrational membrane, and, at least, one composite capacity. Additional details with respect to nano-filtrational the block indicated are given below (utilized materials and methods).

In accordance with the preferable version of the realization of present invention, contaminated the water indicated can be selected from: the following water, obtained based on the petroleum and gas wells; the forced water, obtained based on the recovery of water down the surface together with the hydrocarbons, shaken beside the bore hole for the maintenance the value of pressure against the appropriate levels; effluents of petroleum refineries, waters of those entering based on the enterprises of petrochemical industry; ground water of the oil-refining and/or petrochemical industry.

In accordance with the preferable version of the realization of present invention, adsorptive the block indicated and nano-filtrational the block indicated are located before the sequence.

In accordance with one additional preferable version of the realization of present invention, adsorptive the block indicated is located to nano-filtrational the block indicated.

In accordance with the preferable version of the realization of the present invention, indicated polar organic compounds can be: alcohols, such as, for example, methanol, ethanol, 1- propanol, isopropanol, 1- butanol, isobutanol, tert-butanol; ketones, such as, for example, acetone, 2, 3- butanedione, Z-hydroxy-2- butanone, methylethylketone,, methylbutylketone, pentane-2- it, pentane-3- it; glycols, such as, for example, ethylene glycol, diethylene glycol, triethylene glycol; the carboxylic acids, such as, for example, acetic acid, propionic acid, butanoic acid, pentane acid, hexanoic acid or their methyl-substituted derivatives; aldehydes, such as, for example, acetaldehyde, butanoic aldehyde, pentane aldehyde, hexane aldehyde either their methyl-substituted derivatives or their mixture.

In accordance with the preferable version of the realization of the present invention, indicated polar organic compounds can be present before contaminated the water before a quantity indicated, which is been located in the range from 1 part down million to 30000 parts down million, preferably, in the range from 2 parts down million to 20000 parts down million.

In accordance with the preferable version of the realization of the present invention, indicated nonpolar organic compounds can be: the halogenated solvents, such as, for example, tetrachloroethylene ([RSE]), trichloroethylene ([TSE]), dichloroethylene (DCE), vinyl chloride (VC); the aliphatic and/or aromatic connections, such as, for example, methyltertbutyl ether ([MTVE]), ethyltertbutyl ([ETVE]), benzene, toluene, ethylbenzene, xylenes (known as); phenols; naphthalenes; [3- naphtols; antracenes; the linear aliphatic hydrocarbons, which include from 16 to the atoms of carbon or their mixture.

In accordance with the preferable version of the realization of the present invention, indicated nonpolar organic compounds can be present before contaminated the water before a quantity indicated, which is been located in the range from 1 part down million to 30000 parts down million, preferably, that is been located in the range from 2 parts down million to 20000 parts down million.

In accordance with the preferable version of the realization of present invention, the salts of heavy metals indicated can be: chlorides, sulfates, carbonates, bicarbonates, borates, arsenic, chromium, antimony, selenium, mercury, cadmium, cobalt, nickel, lead, manganese, copper, zinc or their mixture.

In accordance with one additional preferable version of the realization of present invention, the salts of heavy metals indicated can be present before contaminated the water before a quantity indicated, which is been located in the range from 0,1 part down million to 40000 parts down million, preferably, in the range from 1 part down million to 20000 parts down million.

In accordance with one additional preferable version of the realization of present invention, contaminated the water indicated can contain salts of alkaline or alkaline earth metals, such as, for example, chlorides, sulfates, carbonates, bicarbonates, borates, sodium, potassium, calcium, magnesium, barium, strontium, gland or their mixture.

In accordance with one additional preferable version of the realization of present invention, the salts of alkaline or alkaline earth metals indicated can be present before contaminated the water before a quantity indicated, which is been located in the range from 0,1 part down million to 40000 parts down million, preferably, in the range from 1 part down million to 20000 parts down million.

In accordance with the preferable version of the realization of present invention, the oil indicated, dispersed or before the emulsion is the complex mixture, which contains:

the linear, branched or cyclic aliphatic hydrocarbons, such as, for example, n-Heptane, 2, 4, 4- trimethyl -1[pentan], 2- methylhexane, n-octane, 2, 4- dimethylhexane, methylcyclohexane, methylcyclohexene; the aromatic hydrocarbons, such as, for example, benzene, toluene, ethylbenzene and xylenes (known as), phenols, alkyl phenols; aromatic polycyclic hydrocarbons (known as IPAs and PAHs, such as, for example, naphthalene, phenanthrene, pyrene,,. Furthermore, the sulfur-containing connections (for example, sulfides, disulfides, benzothiophene, dibenzothiophene), the nitrogen-bearing connections (for example, quinolines, pyridines), the oxygen-containing connections (for example, fatty acids, naphthenic acid), and also trace quantities of metals (for example, nickel, vanadium, cobalt, chromium, cadmium, lead, arsenic, mercury), as a rule, are present before the oil indicated.

In accordance with the preferable version of the realization of present invention, the oil indicated, dispersed or before the emulsion can be present before contaminated the water before a quantity indicated, which is been located in the range from 50 parts down million to 500 parts down million, preferably, in the range from the parts down million to 400 parts down million.

In accordance with one additional preferable version of the realization of present invention, contaminated the water indicated can contain other contaminiating admixtures, such as, for example, chemical additives, generally accepted with the drilling of well.

In accordance with the preferable version of the realization of present invention, microcellular alumosilicate indicated can be selected from zeolites with the mean diameter of times, that is been located in the range from 3,5[A] to 7,5[A], preferably, in the range from 4,5[A] to 7[A].

In accordance with the preferable version of the realization of present invention, zeolites indicated can have molar relationship the oxide of silicon/the oxide of aluminum (SAR), that is been located in the range from 2 to 500, preferably, in the range from 20 to 300.

In accordance with the preferable version of the realization of present invention, zeolites indicated can be selected from, zeolite ZSM-5, zeolite Y, mordenite, Beta-[tseolita], or their mixtures. Zeolite Y is preferable.

In accordance with the preferable version of the realization of present invention, alumosilicate indicated can have the mean diameter of times, which is been located in the range from 25[A] to 500[A], preferably, in the range from to 200[A].

In accordance with the preferable version of the realization of present invention, alumosilicate indicated can have molar relationship the oxide of silicon/the oxide of aluminum (SAR) in the range from 30 to infinity, preferably, it is more or equal in accordance with the preferable version of the realization of present invention, alumosilicate indicated can have a volume of times, which is been located in the range from 0,3 ml/g to 1,3 ml/g, preferably, times in the range from 0,5 ml/g to 1,1 ml/g.

In accordance with the preferable version of the realization of present invention, alumosilicate indicated can have specific surface area (SBet), it is more or equal to 5002/[g], preferably, which is been located in the range from 6002/[g] to 12002/[g].

In accordance with the preferable version of the realization of present invention, alumosilicate indicated can have completely amorphous structure.

In accordance with one additional preferable version of the realization of present invention, alumosilicate indicated can have, actually, amorphous structure.

For purposes of present description and accompanying formula of invention, term “actually, amorphous structure” indicates the material, which despite the fact that it is formed by the amorphous oxide of silicon, it has the regulated structure with the uniform times, organized beside the hexagonal grid, which has structure.

Completely amorphous alumosilicates, which can be predominantly used for purposes of present invention, can be selected from alumosilicates of the type MSA, described, for example, before the European patents 659478 and 812804 and patent of USA 5049536. Their XDR (X- Howe dif f of ractometry -) the spectrum, obtained from the dust, shows completely amorphous structure. Before the above-indicated patents are also described the different methods of obtaining alumosilicates indicated.

As the alternative, completely amorphous alumosilicates, which can be predominantly used for purposes of present invention, can be selected from alumosilicates of the types:

- MSU, described, for example, Of bagshaw and others beside: “Science” (1995), Vol. 269,. 1242-1244; - KIT-1, described, for example, Of ryoo and others beside: “Studies in Of surface Of science and Catalysis” (1997), Nol. 105, pp. 45-52.

Actually, amorphous alumosilicates, which can be predominantly used for purposes of present invention, can be selected from alumosilicates of the type M41- S (for example, alumosilicate, named41), described, for example, Of beck J.S and of others beside: “Journal of Of american Of chemical Of society” (1992), Vol. 114, pp. 10834-10843. In particular, among alumosilicates of the type M41- S it is possible to select relating down the type mS, described, for example, before the international patent publication W0 91/11390. Their XDR the spectrum, obtained from the dust, shows the presence of the regulated structure with the uniform times, organized beside the hexagonal grid, which has structure.

As the alternative, actually, amorphous alumosilicates, which can be predominantly used for purposes of present invention, can be selected from alumosilicates, named:

FSM-16, described, for example, Of inagaki S. and other beside:

“Journal of Of chemical Of society”, “Chemical Of communication” (1993), pp. 680-682; - HMS-3, described, for example, Of tuel and others beside: “Chemistry of Of materials” (1996), Vol. 8, pp. 114-122; - SBA, described, for example, Of huo and others beside: “Chemistry of Of materials” (1996), Vol. 8, pp. 1147-1160.

As noted above, it should be noted that for purposes of present invention especially one should use alumosilicate in the case of the presence of the oil, dispersed or beside this.

For purposes of present invention microcellular or alumosilicate indicated can be used before various forms. In particular, microcellular or alumosilicate indicated can be formed by means of the realization of extrusion,, tableting, granulation, known before the technological level.

In accordance with the preferable version of the realization of present invention, contaminated the water indicated can be held before the contact with microcellular or alumosilicate (“the time of contact with the unfilled layer”) indicated during the period of time, which is been located in the range from 1 minute to 5 hours, preferably, in the range from 2 minutes to 4 hours.

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can possess the water permeability, measured with 22°[S], that is been located in the range from 0,5 l/([m]2[khchkhbar]) to 5 l/([m]2[khchkhbar]), preferably, in the range from 1 l/([m]2[khchkhbar]) to 3 l/([m]2[khchkhbar]).

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can possess surface energy, which is been located in the range from 4 0 mN/m to 8 0 mN/m, preferably, in the range from 50 mN/m to 75 mN/m.

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can have maximum operating temperature, which is been located in the range from 15°[S] to 50°[S], preferably, in the range from 20°[S] to 45°[S].

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can have maximum operating pressure, which is been located in the range from 5 bars to 45 bars, preferably, in the range from 10 bars to 40 bars.

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can have a cutting off off the molecular weight (MWCO) in the range from 150 Dalton to 300 Dalton, preferably, in the range from 200 Dalton to 280 Dalton.

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can have the maximum working pH, which is been located in the range from 1 to 12, preferably, in the range from 1,5 to 11.

In accordance with the preferable version of the realization of present invention, hydrophilic nano-filtrational the membrane indicated can be selected from the polymer membranes, which contain, preferably, poly-dimethyl siloxanes. indicated can be cross-linked or noncross-linked, preferably, cross-linked.

The hydrophilic nano-filtrational membranes, which predominantly can be used for purposes of present invention, are the products, known under the commercial stamps Of selRO® MPS-44 (series 2540, 4040, 8040) of the production Of koch Of membrane Of systems.

The above-indicated hydrophilic nano-filtrational membranes can have a form of homogeneous membranes, asymmetric membranes, multilayer composition membranes, matrix membranes, which include the layer of gel either the layer of liquid or any other known in this area of technology form. Preferably, they have a form of multilayer composition membranes, which contain base layer, porous bearing layer and layer, which contains, at least, one of the polymers, indicated above. The base layers, suitable for this purpose are, as a rule, the flexible, possessing high porosity woven or non-woven materials, which contain such fibers as metallic threads, polyolefin fibers, fibers, fibers, fibers, carbon fibers or their mixtures; are also down the equal degree suitable the porous structures, which contain glass-, ceramics, graphite, metals. Porous bearing layer, preferably, possesses asymmetric porous structure. Porous supporting indicated layers by polyacrylonitrile, by polyesterimide, by triacetate by polyacrylonitrile, can be formed, for example, on by background, by background, by polyvinylidene fluoride, hydrolized of cellulose, by polyphenylene sulfide, by polytetrafluoroethylene, by polyethylene, by polyvinyl alcohol, by the copolymers of trifluoridepolyolefins or by other suitable polymers or by their mixtures.

The above-indicated hydrophilic nano-filtrational membranes can have the form of flat sheets, hollow fibers, tubular membranes, spirally wound membranes or another proper form.

In accordance with the preferable version of the realization of present invention, specific expenditure (kgf of for sq.

the meter of the surface of hydrophilic nano-filtrational membrane before the hour) can lie in the range from 0,5 kg/([m]2[khch]) to 50 kg/([m]2[khch]), preferably, in the range from 0,8 kg/([m]2[khch]) to 30 kg/([m]2[khch]).

In accordance with the preferable version of the realization of present invention, contaminated the water indicated can be directed down the system at a temperature indicated, which is been located in the range from 10°[S] to 40°[S], preferably, in the range from 15°[S] to 30°[S].

In accordance with the preferable version of the realization of present invention, contaminated the water indicated can be directed down the system indicated with by the pH, which are been located in the range from 1 to 12, preferably, in the range from 2 to in accordance with the preferable version of the realization of present invention, contaminated the water indicated can be given down the system under the pressure indicated in the range from 0,5 bars to 35 bars, preferably, in the range from 0,8 bars to 25 bars.

The utilized materials and methods adsorptive block experiment was carried out beyond the experimental installation (i.e., adsorptive block) with the use of a glass column with the Teflon (Teflon®, DuPont) supports and the connections, that contains, at least, one microcellular or alumosilicate. On Fig. 1 is represented the schematic of the experimental installation (i.e., adsorptive block) used, comprised besides:

- feeding (1) by the capacity of equal, approximately 100 l; - the peristaltic delivery pump (2); glass column (3), that contains microcellular alumosilicate; - the manometer (R), intended for the control besides the operating pressure; - detector (4), the intended for the tracking general content of organic carbon ([TOS]); - three-way valve (5); - collector (b) of fractions.

The installation indicated functioned with the feed rate of 1/[den].

Operating temperature they set equalequal of 20°[S].

7. used the operating pressure, equal to 1 bars, pH of solutions supported for the sake of equal to.

Nano-filtrational block and hydrophilic nano-filtrational membranes experiment was carried out beyond the experimental installation (i.e., nano-filtrational block), equipped for the sake of reservoir for the nano-filtration through the stainless steel, capable of containing beside themselves, at least, one spirally wound hydrophilic nano-filtrational membrane by the diameter of 61 mm, with area 1,62 and the characterized by high relation surface/volume.

On Fig. 2 is represented the schematic of the experimental installation (i.e., nano-filtrational block) used, comprised besides:

- with the feeding (1A) capacity about 300 l; - the peristaltic delivery pump (2[a]); - two manometers (Pi) and ([R]2), intended for the control besides the pressure against the entrance/output based on the reservoir (7) for the nano-filtration through the stainless steel; - reservoir (7) for the nano-filtration through the stainless steel, that contains beside itself hydrophilic nano-filtrational membrane; - composite reservoir (lb).

On Fig. 2 it is also noted (8) and (9).

The installation indicated functioned with the feed rate equal to 800/[den].

Supply was accomplished by the cross flow, which made it possible to weaken the phenomena, connected for the sake of the chemical and physical blockage by hydrophilic nano-filtrational. Operating temperature they set equalequal of 20°[S].

Two values of the operating pressure were used: 10 bars and bar, the pH of solutions supported for the sake of equal to 7.

The utilized hydrophilic nano-filtrational membrane was the spirally wound composition membrane and consisted of the located consecutively pairs of the flat membranes, glued with each other across three sides, with the fourfold side, connected with the central channel for the collection of; the membranes then wound around this channel. Two sheets of the membrane were divided by intermediate grid for the draining of. Grid was also established on the side of supply (between the pairs of the membranes) for the purpose of the creation of additional turbulence, which facilitates reduction in the polarization concentration (theoretically, motion relates down the laminar type with Reynolds number, as a rule, being been located in the range from 100 to 3000).

Ratios between areas of top and bottom wings/volume are sufficiently great they are, as a rule, located in the range from 7002/[m]3 to 10002/[m]3.

The physical chemistry properties of the utilized hydrophilic nano-filtrational membrane Of selRO® MPS-44 (series 2540) (Koch) are given before Table 3.

Table 3 active material is polydimethylsiloxane active area,2 \ - 1

Maximum operating temperature, °[S] maximum operating pressure, bar the pH, 2 0°[S] 2-10

Contact angle with the water, ° 34,2

Cutting off off the molecular weight, Dalton is surface energy, mN/m 68, 1

Charge (with the neutral pH) is negative water permeability with 22°[S], l/([m]2[khchkhbar]) 1,3

Stability to the solvents high before the water solvents for purposes of comparison used a hydrophilic nano-filtrational membrane Of desal®-5-DL (General Of electric Of osmotic), its physical chemistry properties were given before Table 4.

Table 4 active material is aromatic polyamide active area,2 1,77

Maximum operating temperature, °[S] maximum operating pressure, bar the pH, 2 0°[S] \ - 1

\ - 1

\ - 1

Contact angle with the water, ° 49, 4

Cutting off off the molecular weight, Dalton 150-300

Surface energy, mN/m 59, 7

Charge (with the neutral pH) negative water permeability with 22°[S], l/([m]2[khchkhbar]) 3, b stability to the solvents the high before the water solvents degree of separation, which can be achieved by hydrophilic nano-filtrational membrane and, therefore, its effectiveness with respect to the preliminarily specific dissolved substance, is expressed by the percent portion of the detainment:

R (%) = (1- sr Cr)100 moreover, sr and cg indicate the concentrations of the dissolved substance before and of the dissolved substance before, respectively.

Sampling for measuring the concentrations was accomplished on the weights. Each testing continued from 2 hours to 4 hours with conducting of sampling each of hour.

Treatment system, which corresponds to present invention on Fig. 3 is represented the system, which contains adsorptive block and filtrational block in accordance with the present invention: the numbers used and the letters have the same value, that also before given higher description Fig. 1 and Fig. 2. on Fig. 3 is not shown the collector (b) of fractions, existing before the adsorptive block, shown down.1, since the water, which passed working to that indicated adsorptive block is directed directly at the point of the feeding reservoir (1A) of nano-filtrational block.

The analytical methods of water were by qualitative and quantitative analyses and organic connections, which are present before the space in the upper part (flying organic compounds - method 5021), and the organic compounds, extracted by solvents (less flying organic compounds - method 3510).

Qualitative analysis for the purpose of the preliminary identification of the predominant organic compounds was carried out by means of gas chromatography and mass spectrometry (GC -Ms).

Quantitative analysis was carried out as far as two methods: gas chromatography (method 8041 and method 8015), directed on to the most representative classes of organic compounds, for example, the equivalents of phenol, and by the chemical method, which made it possible to obtain the number of being present organic compounds, the expressed as general content of organic carbon ([TOS]) (method 415.1).

Number of oxygen-containing organic compounds for the sake of the small molecular weight, such as alcohols, glycols, aldehydes, ketones and carboxylic acids, were determined by the methods AS OF TM202 and of 8260[V].

The following equipment was used for the analysis:

- gas chromatograph, “extraction and catching” (HP of 6890 Agilent) with the detector of ionization, the slit- slitless injector, equipped for the sake of capillary column DB WAXetr (PEG) (length of 30 m, diameter 320 m, the thickness of film 1 m); - the gas chromatograph, “gas-liquid” (HP 5890, a series OF II with the device for the introduction of tests Agilent 7694) by the detector of ionization, the slit- slitless injector, equipped for the sake of column NR -5 (length of 30 m, diameter 320 m, the thickness of film 0,25 m); the analyzer IL550 TOC-NT (Hach), for the analysis of the general content of organic carbon ([TOS]); the conductometer (model 160, Amel Of instruments), intended for conductivity measurement and, thus, salt concentration; the polarograph Of ecaMon 10S from Instran, equipped for the sake of three-electrode cell with the carbon working electrode, platinum auxiliary electrode and Ag/AgCl by reference electrode and intended for the analysis of zinc, cadmium, lead and copper; the spectrometer of the atomic absorption 220 FS Of varian with the graphite injecting burner; - pH-meter model 632 (Metrohm Of herisan).

For the best understanding of present invention and its realization in practice are given below several explanatory examples, which in no case cannot be considered as the limiting volume present inventions.

Example 1 working following water as far as zeolites used the following water, which is characterized BY of 461 mG/l.

Via quantitative analysis before the water indicated they established the presence of connections before the quantity, equivalent to phenol, equal of parts down million.

Were tested zeolites, represented before Table 5. estimation of zeolites indicated conducted in the course of the experiment, realized with the use of experimental installation, shown on Fig. 1.

For this was used glass column (3) with the Teflon (Teflon®, DuPont) supports and the connections, a diameter of 2,5 cm, a length of 3 0 cm, that contains 17 0 g of zeolite.

After 24 hours of elution from the collector (6) fractions sampled of the processed water for conducting the analysis of the remained before it connections: the obtained results are represented before the table table zeolite SAR

,

mG/l the equivalents there is no phenol, parts down million (test as such) zeolite Y CBV of 100 i) 0,353

Zeolite Y CBV of 720 i) 0,264

Zeolite Y CBV of 712 i) 16, 34

ZSM-5 (i) 0,

Mordenite (2) 0, 849

Zeolite FCC [i) 0, 197

Zeolite Y CBV of 780 i) 0,281

zeolite of the production Of zeolyst zeolite of the production Of tosoh zeolite of the production Of grace from the preceding information it is evident that organic compounds are removed not completely; actually, values indicate the presence of organic compounds.

The water, obtained after working as far as zeolite Y CBV 720, they subjected down qualitative and quantitative analysis for determining what organic compounds before it still are present: obtained data are cited before the table b.

Table b organic compound is concentration, parts down million ethylene glycol 31, b acetone 18,2

1- propanol 19, 7

Triethylene glycol 59, 0

Methanol 34, 9

Ethanol 35, 18

Acetic acid 49, 02

The removal of the organic compounds, given before the table b, can be realized, as it is demonstrated before the examples described further, by a course of the water beside the nano-filtrational installation indicated.

An example 2 workings of following water as far as zeolites used the following water, which is characterized BY of 4185 mG/l.

Via quantitative analysis before the water indicated they established the presence of connections before the quantity, equivalent to phenol, equal to 30,59 parts down million.

Following the water indicated they also subjected down analysis as far as the method of gas chromatography and mass spectrometry, the analysis indicated they completed by the analysis of extract of emulsion (including supernatant liquid) by ethyl ether after acidification to=2, acting in accordance with that presented beside: “Standard Of methods of for of the Of examination of Of water and Wastewater” (1998), 20th Of edition, Method No. 5560: the obtained results are given before Table 7.

During the manipulations in accordance with the method of № 5560 indicated, organic compounds, which are present before following the water indicated, they are converted beside the appropriate acids, thus, indicating the origin and, in particular, down the length of the chain of carbon atoms before them.

Table 7 organic acid concentration, parts down million acetic acid propionic acid isobutyric acid butyric acid valeric acid caproic acid given data testify about the obvious chemical complexity of the mixture of the organic compounds, which are present before the following water, and about the number of organic compounds, which include from 2 to 6 atoms of carbon.

Were tested zeolites, represented before Table 8. estimation of zeolites indicated conducted in the course of the experiment, realized with the use of experimental installation, shown on Fig. 1.

For this was used glass column (3) with the Teflon (Teflon®, DuPont) supports and the connections, a diameter of 2,5 cm, a length of 3 0 cm, that contains 17 0 g of zeolite. Before the column gave following the water with the temperature of 20°[S], the operating pressure of 1 bars and=7 with the aid of of the peristaltic pump indicated (2) with the expenditure of water 1 liter day, in order to ensure the time of contact with the unfilled layer of 3,5 hours.

After 24 hours of elution from the collector (6) fractions sampled of the processed water for conducting the analysis of the remained before it connections: the obtained results are represented before Table 8.

Table 8 zeolite SAR

, mG/l the equivalents of phenol, parts down million there is no (test as such) 30,59

Zeolite Y CBV 100 (1) 9,

Zeolite Y CBV of 720 i) 2,

Zeolite Y CBV of 712 i) 26, 00

ZSM-5 (i) 18,20

Mordenite (2) 15,

Zeolite FCC [i) 21, 00

zeolite of the production Of zeolyst zeolite of the production Of tosoh zeolite of the production Of grace from the preceding information it is evident that organic compounds are removed not completely; actually, values indicate the presence of organic compounds, mainly, the organic compounds, which include from 2 to 6 atoms of carbon, which corresponds to the data, represented before Table 7.

The removal of the 7 organic compounds indicated before the Table can be performed, as it is demonstrated before the examples described further, by the course of the water beside the nano-filtrational block indicated.

Example 3 demineralization: the comparison of two hydrophilic nano-filtrational membranes Of selRO®MPS-44 and Desal®-5-DL used the artificial salt solutions before the distilled water. Different single-component solutions for the sake of seven equimolar concentrations of each salt were prepared, in order to compare the effectiveness of the membranes with respect to the detainment of different dissolved substances, which are present before the identical concentrations: salts and their concentrations are represented before Table 9.

Table is 9 concentration, mole/l 0, 0007

0, 0035

0, 007

0, 014

0, 021

0, 028

0, 035

Salt mm,

Dalton is concentration, parts on millions of NaCl 58,4

MgCl2-6[N]20 203,3

Na2S04 Of mgS04• 7[N]20 246,

On Fig. 4 and 5 are represented the results, obtained with respect to the percent portion of detainment for the membrane Of selRO®MPS44 in accordance with the present invention for the solutions of chlorides of magnesium and sodium with different molar concentrations and two different operating pressures.

The represented diagrams show that detainment by the membrane Of selRO®MPS-44 of chlorides very high. Before the presence of dilute solutions the detainment of sodium chloride is somewhat higher than magnesium chloride. With an increase in the concentration the detainment is reduced and it reaches, approximately, constant. In the case Of1[g] the picture is opposite, although less obvious: with an increase in the concentration the detainment a little increases, exceeding the value of detainment for sodium chloride already with the concentration 0,007 mole/l, and it reaches constant value. The detainment Of and MgSCg by the membrane Of selRO®MPS-44 relative to concentration constantly is equal to 100% already at a pressure of 10 bars.

With the comparison for the sake of the membrane Of desal®-5-DL (comparative) effectiveness, reached as far as the membrane, which corresponds to the present invention (i.e., by the membrane Of selRO®MPS-44), becomes even more obvious.

On Fig. b are represented the results, obtained with respect to the percent portion of detainment for the membrane Of desal®-5-DL for the solutions of chloride and sodium sulfate and magnesium with different molar concentrations. On represented on Fig. b to diagram is evident, especially with respect to chlorides, significant worsening in the detainment in comparison with the results, obtained for the membrane Of selRO®MPS-44 in accordance with the present invention.

Example 4 detainment of the polar organic compounds, not removed by zeolites: the comparison of two hydrophilic nano-filtrational membranes Of selRO®MPS-44 and Desal®-5-DL for this purpose used the artificial solutions, which contain polar organic compounds with the small and average molecular weight, not removed by zeolites, as shown before previously represented examples 1-2.

The solutions, which contain only on one component in the concentration equal to 1000 parts down million, with the operating pressure of 10 bars, at a temperature of 2 0°[S] and=7 were investigated with the use of experimental installation, represented on Fig. 2.

Specific expenditure (kgf of per the sq. meter of the surface of hydrophilic nano-filtrational membrane before the hour) was equal to 1 kg/([m]2[khch]).

Table 10 gives the physical chemistry properties polar organic of the compounds used and the values of detainment, obtained with the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 in accordance with the present invention.

Table organic molecular equivalent is detainment, connection, 1000 masses, the diameter of parts on millions of g/mole of molecule, nm methanol 0,504

15,

Ethylene glycol 62, 1

0,561

59, 4

Tert-butanol 74, 1

0,669

97, 6

Me 88,2

0,723

98,4

ether is diethylene glycol 106, 1

0, 670

91, 6

Triethylene glycol 150,2

0,757

97,7

Table 11 depicts the physical chemistry properties polar organic of the compounds used and the values of detainment, obtained with the use of a hydrophilic nano-filtrational membrane Of desal®-5-DL (comparative).

Table 11 organic molecular equivalent is detainment, connection, 1000 masses, the diameter of parts on millions of g/mole of molecule, nm methanol 0,504

Ethylene glycol 62, 1

0,561

Tert-butanol 74, 1

0,669

Me 88,2

0,723

ether is diethylene glycol 106, 1

0, 670

Triethylene glycol 150,2

0,757

The data, represented before Table 11, show that the use of a hydrophilic nano-filtrational membrane Of desal®- of 5-DL (comparative) leads down worsening in the detainment in comparison with the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 in accordance with the present invention.

An example the detainment of the organic compounds, not removed by zeolites, via nano-filtration for the sake of the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 for this purpose used the artificial solutions, which contain polar organic compounds with the small and average molecular weight, not removed by zeolites, as shown before previously represented examples 1-2.

The solutions, which contain only on one component in the concentration equal to 1000 parts down million, with the operating pressure equal to 10 bars and 2 0 bars, at a temperature of 2 0°[S] and=7 investigated with the use of experimental installation, represented on Fig. 2. specific expenditure (kgf of per the sq. meter of the surface of hydrophilic nano-filtrational membrane before the hour) was equal to 1 kg/([m]2[khch]).

Table 12 gives the values of detainment (R), obtained with the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 in accordance with the present invention.

Table 12 organic compound, 1000 parts on millions of R, %, 10 bars R, %, 20 bars AR, %

Ethylene glycol 59, b 68,2

8, b acetone 77,2

82, b 5, 2

1- propanol 86,5

88, 8

2,3

97,7

98, 8

1,1

Given above data show that an increase in the detainment upon transfer based on the operating pressure of 10 bars to the pressure of 20 bars is more, when molecule less and is, therefore, more badly retained by hydrophilic nano-filtrational membrane.

For the larger molecules with the higher values of detainment (87-98%) an additional increase in the pressure does not lead down a considerable increase in the effectiveness (AR, %, it is equal, approximately, 1-2%); for the smaller molecules, based on the other side with an increase in the pressure is achieved the increase, approximately, 10%.

Example 6 detainment of the organic compounds, not removed by zeolites, via nano-filtration for the sake of the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 for this purpose used the artificial solutions, which contain polar organic compounds with the small and average molecular weight, not removed by zeolites, as shown before previously represented examples 1-2.

The solutions, which contain one or two components simultaneously in the concentration equal to 1000 parts down million, in the absence salts of metals or before the presence of salts of metals beside the concentration equal to 3500 parts down million and 7000 parts down million, with the operating pressure of 10 bars, at a temperature of 2 0°[S] and=7 investigated with the use of experimental installation, represented on Fig. 2. specific expenditure (kgf of per the sq. meter of the surface of hydrophilic nano-filtrational membrane before the hour) was equal to 1 kg/([m]2[khch]).

Table 13 gives the concentrations of the being present salts of metals and the values of detainment, obtained with the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 in accordance with the present invention.

Table 13 organic compound, 1 g/l R, %,

without the salt R, %, before the presence of salt the salt is ethylene glycol 59, b 55, 1

NaCl (3500

./[mln]) acetone 77,2

76,2

NaCl (3500

./[mln]) isopropanol 90, 0

88,5

NaCl Of mgCl2 (3500

(3500

./[mln])./[mln]) 97,7

96, 1

NaCl (3500

h. of/[mln]) methanol + ethanol 39, 2

36, 7

NaCl (3500

./[mln]) methanol + ethanol 39, 2

35, 2

NaCl (3500

./[mln]) given above data show that the large mineralization, actually, does not influence the effectiveness of the hydrophilic nano-filtrational membrane Of selRO®MPS-44:

actually, the addition of salt causes only the limited decrease of detainment.

Example 7 detainment of salts of the heavy metals, not removed by zeolites, via nano-filtration with the use of a hydrophilic nano-filtrational membrane Of selRO®MPS-44 research was conducted with the use of artificial of solutions of copper chloride, zinc, cadmium, lead and manganese, not removed by zeolites, in the concentration of equal to 1 part down million, with the operating pressure of 10 bars, at a temperature of 2 0°[S] and=7 beyond the experimental installation, represented on Fig. 2. specific expenditure (kgf of per the sq. meter of the surface of hydrophilic nano-filtrational membrane before the hour) was equal to 1 kg/([m]2[khch]).

It was discovered, that the values of detainment by the hydrophilic nano-filtrational membrane Of selRO®MPS-44 of metals, which are present before the solutions indicated, are located in the range from 98,5% to 99,8%.