Research manager’s report NPK GENOS Pr. Terpugov G.V.
Membrane technique, water hardness and hemp
will prevent climate warming?
Research manager’s report NPK GENOS Pr. Terpugov G.V.
Membrane technique, water hardness and hemp
will prevent climate warming?
Carbon dioxide is the main component of photosynthesis process, as it contains carbon (symbol C in Mendeleev periodic table). Carbon is found in nature in different forms as in free, so in connected state. In connected state carbon forms a part of organic substances, which are found in animal’s bodies and plants. Wax and oil, turpentine and resin, paper and protein, plants’ cell tissue and animals’ sinewy tissue, glucose and starch – all these and many other substances in tissues and juices of plants and animals are carbon compounds.
Majority of flora representatives absorbs only inorganic compounds and СО2 from environment; and they built their body using sun energy owing to carbon. This process is called photosynthesis.
Summary formula of plants’ photosynthesis is represented in the following equation:
Photosynthesis is the only biological process, which passes with increase of free energy and directly or indirectly transform radiant energy of sun into available chemical energy and supply with it all terrestrial organisms (besides chemosynthetic).
Carbohydrates (proteins, lipids, pigments, vitamins other organic substances) are synthesized from generated in photosynthesis glucose with the participation of mineral dissolved in water substances. Glucose is split into carbon dioxide and water with energy release in the process of plants’ cell respiration, i.e. the process of reverse photosynthesis is carried out.
Plants and terrestrial organisms, which inhabit water mass and water surface, are short-lived. While they die off dead organic substance or detritus was formed. One part of this substance was rapidly reprocessed with carbon dioxide release. The other part was found in sedimentary rocks, for example, in coal, limestone and oil, and got out of substance circulation and photosynthetic activity energy of green plants. The third part stayed too long in external environment, as it was in such conditions or chemical compounds which are decomposed by microorganisms very slowly or with difficulty. For example, undecomposed plant residues and turf formation was stored in marshes.
As follows from the above said life on Earth came into existence and exists owing to photosynthetic substance circulation and living organism energy.
Photosynthesis reaction is reversible, i.e. it can be passed with СО2 absorption and О2 release or vice versa with СО2 release and О2 absorption.
Extraction of carbon and its compounds from this circulation was foreseen by the nature for a long period, which allowed and still allows displacing a reversible photosynthesis reaction in direction of СО2 absorption and О2 release.
Thus, carbon dioxide together with oxygen is a limiting gas, which determines life existence on Earth. It is contained as in air, so in water.
Encyclopaedia says, that air is a mixture of gases, Earth atmosphere consists of these gases: nitrogen (78,08%), oxygen (20,95%), inert gas (0, 94) and carbon dioxide (0,03).
Relation of СО2 and О2 in air is:
Thus, О2 content in air in ≈2600 more than СО2 content.
Quite other relation is in water.
Solubility of N2 (nitrogen) in water by 0°С is 23,54 mg/l, and solubility of oxygen by the same conditions is 48,89 mg/l. Solubility of many gases in water according to the order of magnitude doesn’t differ from the solubility of main air components – nitrogen and oxygen. The exceptions are the gases, which are chemically connected with water or strongly dissociate into ions. These are: carbon dioxide - СО2 (solubility 1713 mg/l by 0ºС), hydrogen sulfide – H2S (4670 mg/l by 0ºС), and also sulfur dioxide – SO2 and ammonia – NH3. Quantity of dissolved in water gas reduces with temperature rise.
Consequently, oxygen and carbon dioxide relation in water by 0ºС and in atmospheric pressure is:
As follows from presented data we can draw four conclusions:
As a result what can happen?
In the beginning of XXI century Earth’s inhabitants experience not a crisis that disturbs weak souls, but the greatest turn of scientific human views, what happens only once a thousand years. It’s essential to choose such way of development where human needs were satisfied without prejudice to our future generation and biosphere in whole. Needs should be necessary, but not excessive, the results of human activity in the production of goods and services mustn’t exceed the possibilities of biosphere or, in the other words; its degradation in the result of this activity is inadmissible. Therefore, nowadays humanity sticks to the policy of intensive terracide.
Particularly, СО2 storage in air (with intensity 0,4% per year) in consequence of absorption processes, conversion processes and preferential radiation of infrared light spectrum by СО2 molecules inside Earth atmosphere, “greenhouse effect” is observed – global warming of Earth climate. Transformation of SO2, NOx and other emissions in air can cause acid fogging and acid raining (snowing), as a result it causes corrosion of many inorganic materials (objects), and also suppression and destruction of different flora and fauna objects. Particulate pollutant (dust, smoke, fog) in atmospheric air prevents the penetration of sun rays on Earth surface, as a result fall of temperature on planet. Settling dust on glaciers surface accelerates its melting owing to intensive solar energy absorption. Atmospheric aerosol causes pollution of surface and underground waters (also soil) as a result of its long sedimentation.
Pollution of atmosphere, reservoirs and soils with solid, liquid and gaseous wastes reaches a warning stage, as nonrenewable natural resources (mainly, minerals and fresh water) are exhausted. Further deterioration of ecosphere state can cause far-reaching negative consequences for a man.
Climate change is the most essential problem of humanity, especially, its rate of change grows, and as predicted by specialists, the situation will be becoming worse. Climate change is inseparably linked with degradation of Earth biosphere. In the end, the most vital matter is preservation of life on Earth. There are reasonable apprehensions that Earth can repeat the fate of Mars, possibly, Venus, if not to take prompt measures. That’s why, the discussions about “when it happens and if it happens at all” are for lazy and incurious, more exactly, unconcerned and egoistical people.
The temperature of circumterrestrial space rises before our eyes because of “greenhouse” industrial gas emissions, the climate changes: sharp temperature drop is observed, it snows where it has never been snowing, and arctic ice thickness is reduced on ca. 40% (large unfrozen patch of water was found in north pole), droughts’ recurrence is increased in 8 times, destructive force of hurricanes – in two times, increase of quantity and destructive consequences of floods. These are all the results of short-sightedness, excessive materialism and greediness, and also unwillingness to see and appraise the consequences because of momentary benefits.
Below stated the percentage (%) of atmospheric air pollution by main branches of industry (in brackets the data of 1987):
Power industry 28,5 (26)
Nonferrous metallurgy 21,6 (9,8)
Ferrous metallurgy 15,2 (17,1)
Oil production 7,9 (8,7)
Oil processing 5,1(6,4)
Mechanical engineering 3,6
Coal industry 3,6
Gas industry 3,3
Constructional material production 3,2 (4,9)
Chemical industry 2,7
Food industry 1,5
Defence industry 0,6
Light industry 0,4.
Level of atmospheric pollution remains high in spite of production decrease and shutdowns: in towns of Russia average concentration of nitrogen dioxide, carbon bisulphide, formaldehyde and benzpyrene exceeds maximum permissible concentration (MPC) in air.
The problem of atmospheric pollution is defined, mainly, by high concentration of suspended matters: nitrogen dioxide, benzpyrene, formaldehyde, phenol and hydrogen fluoride. Concentration of suspended matters in air exceeds 1 MPC in 68 towns, nitrogen dioxide – in 94, benzpyrene – in 85, formaldehyde – in 89 towns. There were 70 towns in 1996 (in 1995-80), in which highest concentration of pollutants in air exceeds 10 MPC. Single concentration for 3 and more substances higher 10 MPC was observed in 8 towns (Kemerovo, Krasnoyarsk, Magnitogorsk, Moscow, Novosibirsk, Omsk, Perm, and Syzran).
In 1996 considerable pollution of European territory of Russia (ETR) with lead and cadmium was observed owing to its inflow from other countries. Thus, “import” of these metals in Russia from Poland, Germany and Sweden exceeds in 10 times its “export” from Russia. The reason is prevalence of west-eastern air-mass transport. Amount of lead inflow on ETR is very significant, only from Ukraine is 1100 t/year, from Poland 180 and Belarus 190 t/year, Germany more than 130 t/year. Yearly amount of cadmium inflow on ETR exceeds 40 t, from Poland almost 9 t, Belarus – ca. 7 t, Finland – more than 6 t and Germany – more than 5t. Total part of lead and cadmium falling on ETR from Russian sources is 70%, rest amount comes with air transport from other countries.
International Conference of United Nations Organization (U.N.O.) on climate change on Earth took place in December 1997 in Kyoto (Japan), where special attention was devoted to “greenhouse” gas emissions into the atmosphere. It was noted in the conference that planet temperature will rise on 2-3 degrees in the nearest ten years owing to today’s amount of “greenhouse” gas emissions from industrial productions, and it causes arctic glacier breakup, rise of World Ocean level, mass flood of coastal regions from Petersburg to Tokyo, complete disappearance of island states, desert formation, decrease of harvest and so on.
Speed of warming process and its results can be more unpredictable, if “spiral and always increasing” СО2 release from World Ocean, seas, rivers and reservoirs will start in the result of first “thermal impact” – temperature rise on 2-3 degrees, it means СО2 release because of warming, which was derived from photosynthetic rotation of substances and energy owing to its solubility in water.
Realizing the complexity of “greenhouse” gas problem there was accepted a final protocol after long and hot discussions (the matter was particular obligations for particular countries, and costly reconstruction of industry and change of life style of whole regions), the protocol provides for total decrease of atmospheric “greenhouse” gas emissions on 5,2% in comparison with the level of 1990 year. As provided by the protocol till the period between 2008-2012 years the countries of European Union are obliged to reduce “greenhouse” gas emissions on 8%, USA – on 7% and Japan – on 6% from the level of 1990 year.
In Russia emission of harmful substances was considerably reduced owing to productivity slowdown. In 2000 year gross emission of “greenhouse” gas was below the level of 1990 on 500 mln. t. After a long discussion we were entitled in 2012 year to reach the emission level of 1990 year.
Will Russia manage to fulfill Kyoto agreement?
In our opinion the implementation of Kyoto agreement is blocked because of a complex of social, political, scientific and technical, economical and religious problems. In this article only single scientific and technical, economical aspects of these problems are presented, mainly, relative to energetics.
Energetics defines considerablly the level of economical development. Throughout humanity history energy consumption increased quicker than the population. Thus, if annual population growth in the period of 1960-1975 was 2,1%, so average annual energy consumption growth was 4,3%.
Technical and social-economical progress of any country is closely connected with the level of energy consumption per head, and also lifetime in this country. Pic. 1 and 2 are visual confirmations of this fact.
Pic. 1. Relation between specific energy consumption
and gross national produce in different world countries (* - tons standard fuel).
Pic. 2. Dependence of lifetime on energy consumption.
In the present time about 90% of all consumed in the world energy is produced from fossil organic fuel. More than one third of produced in the world fuel is burned in boilers and furnaces of thermal power station.
In the structure of energy consumption of Russia specific weight of gas increased in the present time to 50%, and in boiler-furnace fuel – to 68,3%. In such industrially advanced regions of Russia, as in Povolzhskiy, Central, North-Caucasian and North-Western regions the part of gas in boiler-furnace fuel reached 77-83% owing to reduction of mazut and coal use in 3 times. In Moscow this index exceeds already 95%. In 1998 year 812,1 kW/h of electric power was produced, by use of coal– 21,9%, mazut – 6,2%, gas – 40,5%, nuclear fuel – 12%, water power – 19,4%. Trend (to use only one type of fuel) undermines energy security not only of separate regions, but the whole country.
Orientation for advanced growth of gas consumption is unjustified and risky measure for reasons of fuel supply and energy security stability. Any functional disorder of gas industry can cause in the end energy crisis and security violation of a country. It’s impossible to cover all fuel needs of Russia only owing to gas supply. It’s necessary as soon as possible to attract other kinds of fuel-energy resources for wide use.
Gas quota of primary fuel-energy resources consumption doesn’t exceed 30% in USA, Italy, Canada and England; in France and Germany – even less than 20%. It’s possible to increase in practice gas consumption in these countries, but these possibilities are restrained by government purposely for reliability assurance of energy consumption and decrease of risk of energy crisis beginning.
There is another complicated problem in Russian energetic besides lop-sided energy budget – is extremely high physical depreciation of main funds. Percentage of physically depreciated (worn) equipment exceeds 50% in power industry, in oil processing – 80%. Prolongation of equipment’s lifetime owing to “filling in holes” on calculated 30 or above-standard 50 years without introduction of new compensating capacity can cause only expensive repair costs and mass breakdown of equipment.
Simultaneous exhaustion of physical resources of pipelines will take place even in countries with successful gas industry.
The declaration by the President of Russian Federation of inner national produce doubling, necessary change of energy budget and depreciated production facilities of energetics will require new thermal power plants to be put into operation, and, consequently, it causes unavoidable increase of emissions, “greenhouse” and other gases release.
It’s necessary to take into account, that transition of power plants from natural gas to mazut or coal will increase total amount of harmful emissions in 10 and 100 times (СО2 – in 1,7 time in comparison with mazut).
Thus, Russia fulfills Kyoto agreement only owing to productivity slow down and production of thermal and electric energy – in comparison with 1990 year, this year is the calculation base of “greenhouse” gas emissions. For example, energy production in 1990 was 441,9 bil. kWh, and in 1998 – only 301,8 bil. kWh.
That’s why, economical development and solving of above mentioned problems of fuel-energy complex of the country makes it impossible for objective reasons to fulfill Kyoto agreement by Russia, if there won’t be found a simple or relatively cheap scientific and technical solving of “greenhouse” gas recovery in the nearest time or more exactly today.
How is it possible to collect СО2, SO2 and other gas emissions?
On industrial scale, gas emissions in thermal power plants, ferrous and nonferrous metallurgy factories, cement plants and chemical plants are purified with filters and cyclones, also with absorptive and adsorptive methods which remove solid particles. Multilink system with the elements of dust and gas collecting makes possible to purify gas emissions on 99-100% from solid particles, on 90-98% from SO2, on 95-98,5% from NxOy (from different nitrogen oxides). Additional amount of СО2 appears in atmosphere during many technological processes in the result of chemical reactions, it’s an essential disadvantage of such processes.
^ 2 collecting!!!
Theoretically, СО2 is effectively collected only in scrubbers with use of water solution Са(ОН)2 (calcium hydroxide). But this method can’t used in practice, as Са(ОН)2 production and СО2 collecting pass according to following reactions:
СаО + Н2О Са(ОН)2
Са(ОН)2 + СО2 СаСО3 + Н2О
Thus, it’s necessary to decompose natural raw materials – limestones (chalk, shell rocks, marble) with СО2 release to receive Са(ОН)2 and collect СО2 with СаСО3 formation, so this method of collecting is senseless.
How else can we receive Са(ОН)2?
Natural and, especially, hard water (water with excessive Са2+ and Mg2+ content) can be raw materials source for СО2, SO2 wet collecting and other gas emissions of thermal power stations. It’s necessary to combine the production of Са2+ and Mg2+ hydroxides with other process – water softening, which is carried out in all plants of energy complex. Ions salts Са2+ и Mg2+ form sludge on the walls of thermal energy plants, it causes (as it seen on puc. 3) increase of fuel consumption and reduction of efficiency of all energy complex. Therefore, water softening is carried out in all thermal and atomic power plants with use of traditional desalting methods – nanofiltration, reverse osmosis, electrodialysis, ion exchange or their combination, and with a rare method of evaporation.
Pic. 3. Thermal energy loss by heat transfer through heating surface
(according to data of Lifescience, Great Britain).
All desalting plants together with purified fresh water produce certain amount of solutions with significant concentration of salts, and even brines. These concentrated solutions should be utilized in production processes or further processed for hard salts production with their further use or safe disposal. It’s necessary to point out, that the problem of brine processing is solved very slowly even in USA and Japan.
In this connection Terpugov and Mynin developed in our company a new technology of membrane separation based on nonequivalent ion transfer of dissolved substances (direct osmose) through semipermeable membrane. In this process a mentioned shortcoming is absent because ions of dissolved substances pass through the membrane.
Mentioned virtues of a new liquid separation method can be explained with schemes of traditional baromembrane process (for example, reverse osmosis) and offered method on the pic. 1.
Pic. 1. Schemes: а) traditional baromembrane method of liquid separation (reverse osmosis), б) offered method, where:
1 – membrane;
r – thickness of concentrated boundary liquid layer;
х1н solution concentration feeding inside the plant;
х1к – solution concentration getting out of the plant;
х2 – solution concentration which has passed through the membrane;
х3 – solution concentration near membrane surface.
The following relation of dissolved substances concentrations is connected with mentioned processes:
for reverse osmosis Х3 Х1К Х1Н Х2;
for a new method of baromembrane separation Х3 = Х2 Х1Н Х1К.
concentration polarization effect is used in our method, that’s why, it’s not necessary to intermix intensively separated solution, vice versa – separated solution velocity along the membrane surface should be slower. It makes possible to reduce energy costs.
Developed technology of nonequivalent transfer or direct osmosis solves simultaneously several tasks:
And, the most important is to connect gas emissions in sparingly soluble salts (СаСО3, CaSO3 и другие), which can be used in building, thus, to eliminate СO2 from photosynthetic substances circulation, which is formed by fuel burning in thermal power stations.
Thus, membrane technology of nonequivalent dissolved ions transfer through the membrane is a scientific and technical base of water softening processes and effective gas emissions purification in different branches of industrial plants.
In this process the mentioned shortcoming is absent because the ions of dissolved substances, for example Са2+, pass through the membrane, but in a traditional reverse osmosis process water passes through the membrane and ions of dissolved substances remain on it. That’s why, brine, which contains all anions and cations of dissolved in initial water substances, is formed in the processes of equivalent dissolved ions transfer (nanofiltration and reverse osmosis), it also complicates its utilization.
Besides unsolved problem of nanofiltration brines, reverse osmosis and traditional electrodialysis prevent another problem-solving of modern heat-power engineering – achievement of stricter technical water indices, right up to deep softening (0,01-0,05 mg-eqv/l and lower).
In the table 1 you can find general requirements for feed water hardness for boilers of different types.
Water requirements for different boiler.
For example, single-stage reverse-osmosis plant with membrane selectivity of 99% (degree of water purification) by usual water hardness 3,5-7 mg-eqv/l makes possible to reduce this index to 0,035-0,07 mg-eqv/l. Comparing this data with the table data it follows that such purification degree is not sufficient for high-pressure boilers.
Application of second stage of reverse osmosis for deeper water softening is, as a rule, economically unreasonable because of reduction of membrane selectivity in 3-5 times, i.e. selectivity decreases from 99% (see above) to 20-30%.
That’s why, in industry ion-exchange plants are used for water softening after reverse-osmosis plants, however, it doesn’t allow always achieving required water quality.
Thus, developed softening technology of nonequivalent transfer or direct osmosis solves simultaneously several tasks:
Besides СО2 collecting from gas emissions at working enterprises it’s required also to reduce or slow down the growth of its content in atmosphere for decrease of “greenhouse” effect. How is it possible to do?
Firstly, we have to keep in mind that the main source of СО2 absorption and О2 release on Earth is the forests of Russia and treat this source quite the other way. It’s necessary on a state level and with participation of UNO:
Last measure will require some expenses for technology reconstruction of pulp-and-paper factories, but it’s quite essential because of productivity slowdown at these factories, see the table 2.
Cellulose production (digestion) by leading factories, thousand t
That’s why; it’s possible in the present time to transfer pulp-and-paper factories to other kind of raw materials (hemp) without cellulose productivity slowdown in Russia. Besides prevailing technology in these factories is sulphate technology (about 50%), it simplifies considerably transfer process from one kind of raw materials to other one.
Hemp is chosen as raw material owing to unique properties, mainly, is TENFOLD excess growth of fiber mass in comparison with wood pulp .
Consequently, 1 hectare of hemp ABSORBS in 10 times more СО2 for one season than 1 hectare of wood. Hemp not only supplies pulp and paper industry with raw materials, but also preserves forests, and slows down climate warming on Earth.
Thus, membrane technology of nonequivalent (direct osmosis) transfer of dissolved in water ions through membrane, water hardness and hemp are, in our opinion, scientific and technical foundation of a whole complex of activities, aimed at problem-solving of “greenhouse” gas emissions.