Installation of a wet-type flue gas desulfurization and the usage of solid substances obeserver

 

(57) Abstract:

Method and installation of the wet type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, after which the absorption liquid containing absorbed thus the sulfur oxide is subjected to neutralization, which includes electoral leaving solid obeserver substances in the neutralization area of the absorbing fluid and selective removal of the above-mentioned zone of neutralization of the absorbing liquid containing water as a main component and the solid products formed by the oxide of sulfur. In the neutralization zone is formed by the upward flow of the absorbing liquid, or, together with the aforementioned upward flow or independently of the upward flow of air or water for the formation of the liquefied pillows limestone particles, thus preventing the deposition of gypsum particles on the limestone and supported reactivity of limestone. The use of the invention posvol zone of neutralization, the presence of the absorbing liquid aluminum and iron does not degrade the quality of the product also improves the quality of the solid products formed by the oxide of sulfur (gypsum), because solid obeserve substance (limestone) is not mixed with particles of gypsum. 5 C. and 25 C.p. f-crystals, 40 ill.

The invention relates to the installation of a wet-type flue gas desulfurization and method using solid obeserve substance, and in particular, to the installation of a wet-type desulfurization of flue gases and to a method of use of solid obeserver substances for economical removal of oxides of sulfur in the combustion gases leaving the combustion equipment such as boilers, high quality desulfurization, reduced capacity for crushing hard obeserver substances, such as limestone, and a smaller decline in the quality of the product because of the aluminum and fluorine components in the absorber.

The existing level of technology

The sulfur oxides (hereinafter referred to simply as SO2) in flue gases produced by combustion of fossil fuels in thermal power plants, etc. are one of the main sources that cause global environmental problems, tacsew to the removal of SO2and development of plants desulfurization of flue gases, are important issues.

As such methods of desulphurization of flue gases proposed various techniques, but the main one is the handling of the wet type. Processing wet type includes sodium, calcium and magnesium ways, using as sinks, respectively, sodium, calcium and magnesium. Sodium how excellent primarily on the reactivity between the absorber and SO2but used sodium components are very expensive. That's why systems desulphurization of flue gases of large boilers in power plants, the most widely used calcium method that uses relatively cheap calcium components, such as calcium carbonate.

Method of desulfurization using such calcium components as the absorbing liquid, in the General case is divided into the system by spraying with a damp wall and bubbling depending on differences in the method of contacting gas and liquid. Although each system has its own outstanding features, the system will spray much more popular and more reliable and n is La three towers: cooling tower for cooling the exhaust gas and the removal of dust, the desulfurization tower for spraying the absorbing liquid in the exhaust to interact with SO2and the tower of oxidation for the oxidation semitecolo calcium formed in the desulfurization tower. Recently developed dobalina system desulfurization (method of oxidation in the tank), in which the desulfurization tower performs the functions of cooling and oxidation and which is now the most popular way system with spray.

Fig. 39 shows an example of a typical odnomestnoi install desulphurization spray. In General, this dobalina desulfurization system includes a housing 1 tower, intake pipe 2, an exhaust pipe 3, the spray nozzle 4, the pump 5 of the absorber, the circulation tank 6, a mixer 7, the blower 8, the desiccant 9, the discharge tube 10 of the absorber discharge tube 11 gypsum feed tube 12 limestone, the dehydrator 13, etc., Several spray nozzles 4 are placed in the horizontal direction, and several layers loaded in the vertical direction. The mixer 7 and the blower 8 is connected to the circulation tank 6 located at the bottom of the desulfurization tower, where the absorbing liquid, whereas strabotomy gas And, produced from a boiler is introduced into the housing 1 of the desulfurization tower from the inlet pipe 2 and out through the exhaust pipe 3. During this process the absorption liquid is pumped from the pump 5 absorbing fluid through the discharge tube 10 of the absorbing liquid and is sprayed into the tower through a set of nozzles 4 for receiving a gas-liquid contact of the absorbing liquid and the exhaust gas A. If this spray SO2selectively absorbed by the absorbing liquid from the exhaust gas And to education semitecolo calcium. Absorbing liquid containing the so formed sanitarily calcium remains in the circulation tank 6, where the agitation mixer 7 sanitarily calcium in the absorbing liquid is oxidized by air supplied by a blower 8, prior to the formation of gypsum S. Obeserve substance, such as limestone D is added to the absorption liquid in the circulation tank 6 through the limestone feed pipe 12. Part of the absorbing liquid in the circulation tank 6, where the limestone D and plaster, re-pumped by the pump 5 of the absorbing liquid to the spray nozzle 4 through the discharge tube 10 of the absorbing liquid, while the other eeenie the spray nozzle 4, fond of exhaust gas and collected by the desiccant 9 located on the upper part of the desulfurization tower.

The above analog has the following disadvantages.

(1) Absorbing liquid contains not only bicarbonate calcium (limestone), which absorbs SO2but a significant amount of gypsum that nothing contributes to the absorption. If the absorbing liquid increases the proportion of limestone to improve the quality of the product, the quality of gypsum reduced to an unusable level.

(2) For grinding of limestone consumed significant energy supply.

(3) When the absorbing liquid are also aluminum and fluorine components on the surfaces of the limestone particles are formed inactive mixture containing aluminum and fluorine, which degrades the quality of desulfurization.

Accordingly, the objective of the present invention is to provide installation and method of desulfurization of flue gases in order to solve the above conventional problems, and economical achievement of higher quality of desulfurization.

Another objective of the present invention is to provide installation and techniques is of FL, produced from solid obeserver substances.

Another objective of the present invention is to provide installation and method of desulfurization of flue gases with high quality desulfurization, is able to reduce the cost of power for grinding solid obeserver substances.

An additional objective of the present invention is to provide installation and method of desulfurization of flue gases with a high quality product that can easily be divided solid obeserve substance contained in the absorbing liquid, and formed from solid obeserver substances solid products.

Other objectives of the present invention will be described in the following examples.

Disclosure of the invention

To achieve the above objectives, according to the first aspect and feature of the present invention is a method of wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, and then absorb the electoral leaving solid obeserver substances in the neutralization area of the absorbing fluid and selective removal of the above-mentioned zone of neutralization of the absorbing liquid, containing water as a main component and the solid products formed by the oxide of sulfur.

Next, a method of wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, which includes oxidation of the absorbing liquid after absorption in her exhaust gas neutralization of the oxidized thus absorbing fluid solid obesityvisit substance that selectively left in the zone of neutralization, the selective removal of solid products formed from the sulfur oxide and the absorbing liquid containing water as a main component, and re-contacting derived thus absorbing liquid containing water as the main component, with waste gas.

There is also the installation of a wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment, such as the absorption liquid, after which absorption liquid containing absorbed thus the sulfur oxide is subjected to neutralization, which includes the neutralization area absorbing fluid for selective separation of solid obeserver substances and selective removal of the absorbing liquid containing water as a main component, and the solid products formed by the oxide of sulfur.

In addition, there is the installation of wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, which includes the absorption zone for contact of the absorbing liquid with the exhaust gas to absorb sulfur oxide from the exhaust gas in the absorbing liquid, the oxidation zone to oxidize the absorbing liquid containing the absorbed thus the oxide of sulfur, the neutralization area to neutralize the aforementioned oxidized absorbing fluid obesityvisit substance, selective separation of solid obeserver Vesennie products formed from oxides of sulphur, and the circulation channel of the absorbing liquid to feed into the absorption zone, absorbing fluid containing water and solids formed from oxides of sulphur.

Solid obeserve substance used in the present invention preferably has the average particle diameter (hereinafter simply mean diameter of particles greater than 0.5 mm, a Substance with an average particle diameter of less than 0.5 mm would impede the Department obeserver substances from the reaction products of oxidation, such as gypsum, and would lead to the reduction of particle size of solid obeserver substances, such as limestone, in the transfer process, after grinding, to install desulphurization of flue gases. More preferably, the solid obeserve substance had average particle diameter is more than 1.0 mm Solid obeserve substance with an average particle diameter of more than 10 mm would reduce reactivity to neutralize the absorbing fluid, which absorbs SO2in the exhaust, and besides, it was Easter would feed tube solid obeserver substance, which is connected with the neutralization area installation of desulphurization of flue gases. Accordingly, per the C from 0.5 to 10 mm However, the present solid obeserve substance may contain particles of 0.5 mm or less, because this desirable average particle diameter is a standard, which is not limited strictly.

Exhaust gas contains many kinds of fine components and in particular in the case of boilers burning coal, a huge amount of ash. This ash is mainly removed by the dust collector before the desulfurization tower, but partially entered into the desulfurization tower and captured raspilyaj absorbing liquid. Ash contains aluminum (Al) component, part of which is dissolved in the absorbing liquid, when it is absorbed SO2by reducing its pH value. On the other hand, contained in the exhaust hydrogen fluoride (HF) is captured by the sprayed absorbing liquid and in the presence of the above-described Al component reacts with the limestone to form mixtures containing aluminum and fluorine, are usually represented, for example, chemical formula: CaAlF3(OH)2CaF2. Such mixtures are deposited on the surface of the limestone particles, which reduces the reactivity of the limestone. The inventors have found that this reaction is not associated with deletestream with an average particle diameter of more than 0.5 mm, when each limestone particle in the zone of neutralization in contact with others and abrasions. More small limestone particles are suspended in the absorbing fluid due to the smaller diameter of its particles and do not contribute to this phenomenon.

In the present invention it is desirable to apply solid obeserve substance in the neutralization area in the form of a suspension or an air transfer in the dried state.

The volume of the solid obeserver substance subject to filing in the neutralization area, is governed by the dispenser or operation on-off crushers for hard obeserver substances, whereas the particle size of solid obeserver substances controlled by adjusting the speed of the crusher, etc.

Limestone is a typical example of solid obeserver substances used in the present invention. The so-called limestone, used here, means a sedimentary rock containing calcium carbonate as the main component, and further comprises in the present invention such rocks, which contain as limestone magnesium carbonate. Accordingly, when used herein, the limestone is also included dolomi MESI, which affect reactivity desulfurization, it is desirable that CaCO3having a higher reactivity, was naked on a solid surface by grinding limestone. However, since the solid obeserve substance with particles of smaller size easier is included in the solid products, such as gypsum, these smaller particles must be pre-separated and removed, even if they have higher reactivity. On the other hand, excessively large particles would spoil the feeding zone of the solid obeserver substances, therefore, it is desirable that the feed area was equipped with a filter or a cyclone for separating solid obeserver substances.

The main reactions occurring in the installation of desulphurization of flue gases according to the present invention are described as follows. The following formulas (1) to (3) reactions are presented as a typical reaction for a better understanding of the present invention, and it is believed that all reactions in the installation of desulphurization of flue gases do not always correspond to formulas (1) to (3).

Response by these formulas (1) to (3) will be described in the example in which the solid obeserver sostavlyajushie) absorbs SO2in the exhaust before the formation of H2SO3, which is then oxidized by air to H2SO4(diluted sulphuric acid). H2SO4neutralized by CaCO3prior to the formation of gypsum (CaSO42H2O).

(Reaction absorption)

H2O + SO2= H2SO3(1)

(Oxidation reaction)

H2SO3+1/2O2= H2SO4(2)

(Neutralization reaction)

H2SO4+ CaCO3+ H20= CaSO42H2O + CO2(3)

The resulting gypsum is collected and used as an industrial material, such as dry plaster. A significant inclusion of limestone gypsum undesirable affects the quality of the product. Thus, in conventional obestsenivaya installations it is necessary that the concentration of limestone in the absorbing liquid level at which the IDT neutralization reaction, is maintained below a predetermined value (for example, about 1/100 of the concentration of gypsum). The absorbing liquid containing gypsum and limestone, can be processed through a separator, such as a wet cyclone, to selectively collect the gypsum in the absorbing liquid. However, this separation is inefficient, because the flue gases, it is small, and, moreover, the separating device of the road.

According to the present invention, the particles of limestone selectively remain in the zone of neutralization, where the installation of desulphurization of flue gases pH value of the absorbing liquid is reduced due to the absorption of sulfur oxide and water and formed from the sulfur oxide plaster are removed from the system. This allows us to improve the quality of the product, maintaining at the same time, the quality of the plaster. In the real process of the present invention limestone used for neutralization of the absorbing liquid, which absorbs SO2in the exhaust, has a larger average diameter of 0.5 mm and preferably 1 mm or more, so the limestone and gypsum easily separated (gypsum has a typical average diameter of 30 to 100 μm).

Further, according to the present invention, since the use of limestone with a relatively large particle diameter, there is no need to crush it finely, eliminating fine crushing and saved power for crushing.

In the present invention it is possible to load limestone in the neutralization area sufficient for consumption during continuous operation lasting about 2 buesa precise control of the supply of limestone in the area of neutralization, even if the supply of the exhaust gas increases and the pH value of the absorbing this exhaust gas absorbing fluid is markedly reduced.

The reaction according to the formula (3) occurs on the surface of the limestone particles in the zone of neutralization. Continuous contact of the absorbing liquid containing H2SO4with limestone particles, supports the reaction (3) and improves the quality of desulfurization. When absorbing the liquid flows down from the top of the limestone layer in the download area of limestone, the limestone layer is compacted prior to the formation of regions where the absorption liquid flows slowly and not flowing, which reduces the quality of desulfurization. In order to solve the problem of sealing the limestone layer, the absorbing liquid, for example, flows in the zone of neutralization with a certain flow rate or faster from the bottom of the limestone layer up for liquefaction limestone particles, which increases the quality of the product.

Since in the present invention, it is difficult to determine the height of the limestone layer and the conditions for the liquefaction of limestone at the level of neutralization, although and forms a liquid cushion limestone layer, there is a possibility that the absorption liquid Izbira region, in contact with exhaust gas does not change, if the absorbing liquid flows into the limestone layer in the main part of lesser height (the part containing a smaller amount of limestone), the ratio of limestone to the absorbing fluid is excessively reduced. This is reflected in the lowering of the pH value of the absorbing liquid supplied to the area that is in contact with exhaust gas, but also the quality of the product.

The height of the limestone layer in the whole area of neutralization can be almost aligned (or uniform) and thereby to prevent deterioration of the quality of desulfurization by using more than one of the following methods: the insufflation gas, such as air, into the limestone layer in the neutralization area, release the liquid, such as water, under pressure into the limestone layer or mixing of limestone through mixing equipment. You can also replace the simple injection of gas into the limestone layer to align (or uniform) the height of the limestone layer in the whole area of neutralization, to inject gas to the portion where the absorbing liquid is released under pressure from the bottom up in the neutralization zone to supply gas into the limestone layer together with absorb the, equipped with a mixing blades or scrapers in the zone of neutralization, the rotation of the neutralization zone, etc.

More preferably the alignment of the height of the limestone layer in the whole area of neutralization is carried out by using more than one of the following methods: first of all, the discovery of the liquefied state of the limestone in many points by defining more than one factor selected from the group consisting of a pressure loss in the limestone layer in the set of points of liquefaction, the concentration of solids, specific gravity and viscosity of the absorbing fluid (pressure loss is reduced in the weak points of liquefaction), followed by the injection of gas, such as air, or vusanje fluid, such as water, under pressure into the limestone layer at points where the conditions of liquefaction is bad, or the mixing of limestone through the mixing device.

The loss of P pressure to the liquefied air bags in the General case is expressed by the following formula:

P = (specific gravity of limestone - specific gravity of the absorbing liquid) x (height of the limestone layer) x (1 - porosity).

Porosity in this formula is the value in the state of takuseshi, and accordingly the height of the layer of limestone in the state of stationarity can be defined by the same formula. In other words, since the proportion of limestone known (about 2.7) and its porosity in the condition of stationarity is about 0.4, while depends on the particle shape, the height of the layer of limestone is obtained from the definition of loss of pressure P and specific gravity of the absorbing liquid. Further, since the specific gravity of the absorbing liquid is associated with the concentration of particles (essentially the concentration of the particles of gypsum) or the viscosity of the absorbing liquid, such concentration or viscosity can be determined instead of the specific weight.

In the absorbing liquid is maintained mixing limestone particles, and the influence of the contact of these components is increased by using more than one of the following methods: the insufflation gas, such as air, into the limestone layer in the neutralization area, release the liquid, such as water, under pressure into the limestone layer or mixing of limestone through mixing equipment.

Further, part of the CO2dissolved in the absorbing liquid is excluded to maintain the neutralization and improve the quality obesere is ASEE the invention is applicable also to the installation of desulphurization of flue gases, equipped with outer tower oxidation. This type of installation the product contains a cooling tower for cooling and removing moisture from the exhaust gas, a desulfurization tower for spraying the absorbing liquid to react with SO2in the exhaust and the tower of oxidation for the oxidation semitecolo calcium formed in the desulfurization tower. In the installation of desulphurization of flue gases from the outer tower oxidation according to the present invention following main reactions take place.

Absorbing liquid (containing water as the main component) absorbs SO2in the exhaust before the formation of sulfurous acid (H2SO3), followed by reaction with sanitarily calcium (CaSO31/2H2O) to obtain hyposulphite of calcium (Ca(HSO3)2). Then the hyposulphite of calcium reacts with the limestone in the area to neutralize education semitecolo calcium. Received sanitarily calcium is again supplied to the absorption zone for reaction with H2SO3, which is formed by absorption of SO2in the exhaust. On the other hand, part semitecolo calcium is fed into the oxidation tower, where it is subsequently added sulfur >O).

(Reaction absorption)

H2O + SO2= H2SO3< / BR>
CaSO31/2H2O+H2SO3= Ca(HSO3)2+1/2H2O

(Neutralization reaction)

Ca(HSO3)2+ CaCO3= CaSO31/2H2O +CO2< / BR>
(Oxidation reaction)

CaSO31/2H2O + 1/2O2+ 3/2H2O = CaSO42H2O

Brief description of drawings

Fig. 1 is a conditional form odnomestnoi installation of a wet-type flue gas desulfurization according to example 1 of the present invention.

Fig.2 is a section along line a-a in Fig.1.

Fig.3 is an enlarged view of the feeding limestone pipe according to Fig.1.

Fig.4 is an enlarged view of a modified zone of neutralization in Fig.1.

Fig.5 is a modification of Fig.4, taken along the line b-b.

Fig. 6 is a graph representing the relationship between the pH value of the absorbing liquid and the percentage desulfurization or concentration of limestone in plaster in example 1 (solid line) and in the comparative example 1 (dashed line).

Fig.7 is a graph representing the relationship between the flow velocity of the upward flow of the absorbing gidrostroitelei relationship between the concentration of the components Al and F in the absorbing fluid and the ratio of desulfurization in example 1 (solid line) and in the comparative example 1 (dashed line).

Fig.9 is a flow diagram of the installation of desulphurization in example 2.

Fig. 10 is a graph representing a change over time in the ratio of desulfurization in example 2, and the solid line shows the result obtained when the limestone layer remains in the neutralization device is stationary, and the dotted line shows the result obtained when the limestone in the device neutralization mixed.

Fig. 11 is a conditional form used in example 2, the neutralization device equipped with a mixer.

Fig. 12 is a conditional form is used as the neutralization device in example 2, rotating drying kiln.

Fig. 13 is a conditional form is used as the neutralization device in example 2, the installation of desulphurization, where the circulation tank is installed scraper.

Fig. 14 is a conditional form used in example 3, the installation of desulphurization.

Fig. 15 is a graph representing the relationship between the concentration dissolved in the absorbing liquid oxygen after neutralization ratio of desulfurization in example 3.

Fig. 16 awlays tower.

Fig. 17 is a conditional form of the installation of desulphurization with jet bubbling used in example 5 according to the present invention, in which the exhaust gas is blown under pressure into the absorption liquid through a pipe.

Fig. 18 is a conditional form of horizontal (or lateral) installation method used in example 6 according to the present invention.

Fig. 19 is a conventional type of installation method used in example 7, in which the absorbing liquid is supplied carboxylic acid or its salt.

Fig. 20 is a graph representing the relationship between the ratio of liquid-gas (L/G) (i.e., the ratio in volume of the sprayed absorbing liquid to the exhaust gas) and the coefficient of desulphurization, when the absorbing fluid is changed concentration moravcikova sodium in example 7.

Fig. 21 is a graph representing a change in the coefficient of desulphurization, when the pH value of the absorbing liquid inlet device neutralization controlled by the amount of limestone in example 8.

Fig. 22 is a flow diagram used in example 9 installation of desulphurization of flue gases, where the relationship between the time of installation of desulfurization and the ratio of desulfurization, moreover, a solid line (a) and dashed line (b) shows the relationship between time and rate of desulfurization, respectively, in example 9 and comparative example 3.

Fig. 24 is a graph representing the relationship between the time of installation of desulphurization and coefiicients desulfurization, and a solid line (a) and dashed line (b) shows the relationship between time and rate of desulfurization, respectively, in example 10 and comparative example 4.

Fig. 25 is a conditional form used in example 11 installation of desulphurization, which in the limestone layer is also blown into the air.

Fig. 26 is an enlarged view shown in Fig. 25 device neutralization.

Fig. 27 is a graph representing the variation over time in the ratio of desulfurization installation of desulfurization, and a solid line (a) shows the change when used in example 11 installing desulphurization stops working for a certain period of time and then starts again, the dashed line (b) shows the same change in used in comparative example 5, a typical installation (shown in Fig. 39), and the dash-dotted is continuously injected air.

Fig. 28 is a conventional type used in example 13 installation of desulphurization, in which the neutralization device is located near the building of the tower desulfurization, and limestone layer in the device of neutralization is stirred by the stirrer so that the height of the layer is aligned.

Fig.29 is an enlarged bottom part used in example 14 of the circulation tank, which under directed down a vertical tube attached to the distribution pipe, equipped with a conical reflective plate.

Fig. 30 is a graph representing the relationship between the angle X of the reflective plates to the plane of the bottom of the circulation tank and the ratio of desulfurization in example 14.

Fig. 31 is a modification of example 14, in which the conic reflective plate installed above the sloping upwards tubes attached to the distribution pipe.

Fig. 32 is a cross-section of the upper part of the vertical tubes in Fig. 30 and 31.

Fig. 33 is a conventional type used in example 15 installation of desulphurization, in which the neutralization device placed independently next to the circulation tank, and only cha is the neutralization device.

Fig. 34 is a conventional type used in example 16 installation of desulphurization, in which next to the circulation line of the absorbing liquid to the nozzles is air line absorbing fluid connected with the upper part of the circulation tank.

Fig. 35 is a conventional type used in example 17 according to the present invention installed desulphurization, equipped with an external oxidation tower.

Fig. 36 is a conventional view of a typical installation of desulphurization of flue gases supplied external oxidation tower.

Fig. 37 is an example of primary limestone supply according to the present invention.

Fig. 38 is another example of the system of primary limestone supply according to the present invention.

Fig. 39 is a conditional plain odnomestnoi installation of a wet-type flue gas desulfurization.

Fig. 40 is an image zone of neutralization according to the claimed invention.

Description of the preferred execution of the invention

The present invention will be now described in detail by executions, but not intended to limit these wypolnenije shown in Fig. 39 conventional desulfurization tower presents in this example, the apparatus comprises a housing 1 tower, intake pipe 2, an exhaust pipe 3, the spray nozzle 4, the pump 5 of the absorbing liquid, the circulation tank 6, a mixer 7, the blower 8, 9 desiccant, etc. and also provided with a collecting liquid plate 14, an introduction pipe 15, the pipe 16 shown in Fig. 2, and distributing pipe 17 of the circulation tank 6 for collecting drops of the absorbing liquid, the education of its upward flow from the bottom to the top layer 19 of the limestone particles loaded in the lower part of the circulation tank 6, and liquefaction of the limestone particles in the absorbing liquid.

Exhaust gas And leaving the boiler (not shown), is introduced into the housing 1 of the desulfurization tower from the inlet pipe 2 and is removed from the exhaust pipe 3. During this process of absorbing the liquid pumped by the pump 5 of the absorbing liquid sprayed into the desulfurization tower through a lot of spray nozzles 4 for implementation of the contact gas - liquid between the absorbing liquid and the exhaust gas A. Thanks droplets absorbing fluid selectively absorb SO2. Before the formation of sulphurous acid. Droplets plate 14, installed on the circulation tank 6. Falling on collecting liquid plate 14 absorbs the liquid is collected and fed to the bottom of the circulation tank 6 through the introduction pipe 15. On the way sulfurous acid in the absorbing liquid is oxidized to sulfuric acid oxidizing air, which is blown blower apparatus 8.

To the bottom of the introduction pipe 15 is attached distributing pipe 17, which allows the absorbing liquid to rise in the circulation tank 6 uniformly across its plane. In Fig. 2 shows the construction of the distributing pipe 17. Fig.2 is a view of the bottom of the circulation tank 6, provided with a distributing pipe 17, which is designed to allow the absorbing liquid to rise up from the bottom of the circulation tank 6 uniformly across its bottom plane.

Distributing pipe 17 is set to a uniform distribution across the bottom plane of the circulation tank 6, while the absorbing liquid is directed to the introduction pipe 15 enters the pipe 16, and then fed into the distributing pipe 17. Distributing pipe 17 has many distribution holes 18, through which the absorbing what I education in it upstream. Sulphurous acid and limestone react to the formation of gypsum in the limestone layer 19, which oijala in the absorbing liquid in the circulation tank 6. The pH value of the circulating absorption liquid is constantly measured by the meter 21 pH values.

Neutralized thus in the limestone layer 19 in the circulation tank 6 absorbing liquid was found after a certain pH value is again fed to the spraying nozzles 4 from issue 20, located in the upper part of the circulation tank 6, through the discharge tube 10 of the absorbing liquid for selective absorption of SO2in the exhaust A. Part of the absorbing liquid is supplied to the dehydrator 13 to collect gypsum With.

Limestone D is supplied to the circulation tank 6 through the limestone feed pipe 12. Limestone particles in suspension or in dry form from limestone feed pipe 12. When through the limestone feed pipe 12 into the tower compressed air is dried limestone, because of the presence of vapor absorbing liquid because the temperature in the circulation tank 6 of about 50oC, dry limestone hydrated and sticks in the form of fat F on the surface nutrigo on the wall, would cause clogging of limestone feed pipe 12, it is desirable to provide a flushing vodorazreshimye nozzle 22 for periodic washing of the walls of the limestone feed pipe 12 to remove lime deposits F. This flush Vodorezova nozzle 22 for periodic washing of the walls of the limestone feed pipe 12 to remove lime deposits F, although not shown in the drawings, optionally used in the examples which will be described below.

Although sulphurous acid and limestone react in the liquefied limestone layer 19 to the formation of gypsum from the circulation tank 6 through 20, located in the upper part displays only particles of gypsum and water, because the particles of gypsum smaller than the particles of limestone, and limestone selectively remains in the circulation tank 6.

When the circulation tank 6 has an annular shape, can be applied is shown in Fig. 4 and 5 introduction pipe 15, the pipe 16 and the distributing pipe 17. Fig. 4 is a side view of the circulation tank 6, and Fig. 5 is a section along the line b - b in Fig. 4. The pipe 16 is connected with the bottom side surface of the introduction pipe 15, while it has many distribution is the aka, that the rate of injection of the absorbing liquid from the distributing holes 18 of each tube 17 is supported above the specified value.

As a distributing tube 17 with distribution holes 18 can be used distribution nozzle used in the zone spray for spraying the absorbing liquid after removing a nozzle 4.

To install the product according to example 1 was carried out checking desulfurization limestone with an average particle diameter of 2 mm Concentration of SO2in the exhaust at the inlet of the installation of desulphurization was 1000 ppm. The volume of air before injection into the circulation tank 6 was 30 times more volume SO2in the exhaust based on molar relationships. The relationship between pH after neutralization and percentage desulfurization, as the concentration of limestone in plaster, shown by the solid line (a) in Fig. 6. Adjust pH after neutralization was carried out by a number of limestone. Although the percentage of desulfurization increases with increasing pH value of the absorbing liquid, the concentration of limestone in the plaster shows a small increase of the plaster, the output of the circulation tank 6 from an edition of 20, which is located in its upper part, has high quality.

The speed of the upward flow of the absorbing liquid was controlled by changing the sectional area of the limestone layer 19 (the amount of limestone is kept constant).

Fig. 7 is a graph representing the relationship between the velocity of the upward flow of the absorbing liquid in the limestone layer 19 and a percentage of desulfurization. With the increase of the velocity of the upward flow of the absorbing liquid percentage desulfurization improves and remains almost constant when the speed of the upward flow of 6 cm/s Speed of the upward flow is a value obtained by dividing the volume of liquid flow sectional area of the limestone layer 19.

When the concentration of SO2in the exhaust in the intake pipe 2 of the desulfurization tower varies from 100 to 5000 parts per million, the percentage of desulfurization increases with the increase of the velocity of the upward flow of the absorbing liquid in the limestone layer 19 when any of the above concentration and remains almost constant when the speed of the upward flow of 6 cm/sec. Preferably the speed going up the percentage value desulfurization decreases at a lower rate, and the pressure loss increases at a higher speed than the above-described preferred range.

When equimolar quantities of AlCl3and NaF are added together as a reagent in absorbent liquid to change the concentration of Al and F components in a given height of the limestone layer and the diameter of the particles of limestone, the percentage of desulfurization is changed, as shown by the solid line (a) in Fig. 8. A small decrease in percentage of desulfurization was observed even when the concentration of Al and F components equal to 5 mmol/L.

Although in this example, the absorption liquid which is withdrawn from the circulation tank 6, is fed directly to the nozzles 4 and the dehydrator 13, limestone derived from the circulation tank 6 of the absorbing liquid may be separated by a separator, which is not shown. The resulting absorption liquid from which removed the limestone serves to collect gypsum of high quality.

Since the installation of desulphurization stops on periodic audits contained in different blocks and devices of the limestone in the circulation tank 6 is removed and when neobhodymuyu layer 19 oijala. In other words, upload limestone in a static state is very difficult, but easy in the liquefied state, together with the liquid. However, under these conditions, part of the limestone with a simple deletion is still in the zone of neutralization, because the absorbing liquid is excreted easier than limestone. Accordingly, in order to completely remove limestone from the zone of neutralization, it is possible to allow the absorbing fluid and limestone to settle prior to the deposition of limestone in the sediment and re-submit in the area neutralize the liquid. Remote so limestone is not released wasteful, but is crushed to reduce to some extent the diameter of the particles to significantly expose the reaction components on the surface of particles for reuse.

Comparative example 1.

In the same as in example 1, the installation of desulphurization was tested quality desulfurization limestone with an average particle diameter of 10 μm. Due to the smaller diameter of the particles of limestone it in this comparative example, suspended in absorbing fluid and does not constitute any of its liquefied pillows, as observed in example 1. The relationship between the pH value of the Yak in plaster, shown by a dotted line (b) in Fig. 6. If the pH after neutralization remains the same, the percentage of desulfurization is the same as in example 1. It appears, however, that the concentration of limestone in plaster higher than in example 1, and with increasing pH, the concentration increases and the quality of the gypsum is deteriorating.

When equimolar quantities of AlCl3and NaF are added together as a reagent in absorbent liquid to change the concentration of Al and F components in a given concentration of limestone in the absorbing liquid, etc. , the percentage of desulfurization is changed, as shown in dotted

line (b) in Fig. 8. The percentage desulfurization significantly lower compared with the same amount of example 1.

Example 2.

Technological scheme of the method used in example 2 shown in Fig. 9. Unlike example 1, in which the absorbing liquid is neutralized in the circulation tank 6, unit 23 of neutralization can also be installed outside of the absorbing liquid in the circulation tank 6, as is the case in this example 2. As in a conventional desulfurization tower, pakatan the th nozzle 4, the pump 5 of the absorbing liquid, the circulation tank 6, a mixer 7, the blower 8, 9 desiccant, etc. and have next block 23 neutralization to increase the pH value of the absorbing liquid, the pH value of which is reduced due to the absorption of SO2in the exhaust A.

As in example 1, the absorption liquid is selectively absorbs SO2in the exhaust And before the formation of sulphurous acid, which is then oxidized in the circulation tank 6 to obtain sulfuric acid. Absorbing liquid containing sulfuric acid, via a pump (not shown) is supplied to the block 23 neutralization and neutralized it with limestone to form gypsum. Part of the absorbing liquid after neutralization is served in the dehydrator 13 and dehydrated to collect gypsum C. on the other hand, neutralized thus absorbing the liquid returns to the spray nozzles 4 for selective absorption of SO2. Limestone D is served in the block 23 neutralization through limestone feed tube 12.

As in example 1, when dried limestone is fed with compressed air into the tower through the limestone feed pipe 12, to avoid deposits of hydrated limestone 22 to periodically wash the inner walls of the limestone feed pipe 12, to remove lime deposits.

When using the install method on this example checks were performed desulfurization. The concentration of SO2in the exhaust And intake tower desulfurization was 1000 ppm. Limestone (with an average particle diameter of 5 mm) pre-loaded in block 23 neutralization in equimolar amount to the SO2in the exhaust, i.e., in the amount sufficient for desulfurization for two hours, and then fed back through the supply pipe 12 in the amount of 0.97 molar ratio corresponding to the SO2in the exhaust. The volume of air injected into the circulation tank 6 was 30 times more volume SO2in the exhaust based on molar relationships.

The change in the percentage of desulfurization in time shown by the solid line (a) in Fig. 10, when the limestone layer 19 allow him to remain in the block 23 neutralization. In the beginning there was a higher quality product, which decreased over time. The reason it was found that the particles of gypsum deposited on the surface of the limestone particles in the block 23 neutralization, thereby reducing the reactivity of limestone. Then contrtol mixer 25, it is shown in Fig. 11. The change in the percentage of desulfurization in time after such improvement is shown by a line b in Fig. 10. It was found that the quality of the product is not reduced, but remains a long time on a higher level. When the concentration of SO2in the exhaust And on the issue of the desulfurization tower was changed from 100 to 5000 parts per million, as desulfurization by using a stirrer 25 stayed a long time at a higher level at any concentration.

As the block design 23 neutralization can be used in any design in which the limestone with an average diameter of 1 mm or so shaken in the absorbing liquid. In block 23 neutralization, as shown in Fig. 11, the absorbing liquid containing sulfuric acid is supplied from the circulation tank 6 in block 23 neutralization through the pipeline 10 and neutralized with limestone D with stirring by a stirrer 25. Due to the smaller diameter of the particles of gypsum compared to the diameter of the particles of limestone particles of plaster and water is fed from the upper part of the block 23 neutralization to the spraying nozzles 4 and the dehydrator 13, whereas the limestone D selectively octets and absorbing fluid, can be used in any design in which there is no substantial draining limestone particles down.

Hereinafter, may be different than using a mixer 25, preventing the deposition of particles of gypsum on the surface of the limestone particles with bubbling fluidised bed gas, such as air, between the limestone particles to control their deposition.

As block 23 neutralization can also be used rotating the drying oven 26, shown in Fig. 12. In this case, the downloaded limestone (not shown) is shaken due to the rotation of the drying furnace 26. On the other hand, Fig. 13 is a conditional form of the installation of desulphurization, in which the block neutralization at the bottom of the circulation tank 6 has a scraper 27.

When used as shown in Fig. 12 oven 26, it is possible to control the residence time of the absorbing liquid in the furnace 26 by changing the speed of rotation of the furnace 26 instead of adjusting the speed of rotation of the agitator 25, or a return of part of the absorbing liquid at the inlet of the furnace 26 through line 30 through valve 29 located at the discharge from the furnace 26, instead of adjusting the volume of the absorbing liquid level reservoiring outside the desulfurization tower, at the bottom of the circulation tank 6 has a scraper 27, as shown in Fig. 13, the limestone particles (not shown) are loaded into the circulation tank 6, while the concentration of SO2on the issue of the desulfurization tower can be controlled by the stirring speed of the scraper 27. Fig. 13 shows an example in which the outside of the tower installed desulphurization limestone-gypsum separator 31.

Example 3.

Although in example 2, block 23 neutralization is installed outside of the desulfurization tower, you can also download the limestone D in the lower part of the circulation tank 6, and the output of him absorbing liquid is neutralized through the layer 19 of limestone D for submission to the separator 31, as shown in Fig. 14. Oxidized absorption liquid is neutralized with a layer 19 of limestone D and fed into the separator 31 to separate gypsum and limestone, making the absorbing liquid with a lower content of limestone is served in the dehydrator 13 for dehydration and collection of plaster C. on the other hand, the absorbing liquid with a higher content of limestone is again fed to the spraying nozzles 4 in the housing 1 tower for selective absorption of SO2.

It is preferable to remove osedax the x2">

The quality of the product was checked when the volume of air blown in is shown in Fig. 14 the circulation tank 6, in the range from 10 to 100 times the volume of SO2in the exhaust and with the determination of dissolved oxygen concentration in the separator through meter 33 dissolved oxygen. The relationship between dissolved oxygen and percentage desulfurization shown in Fig. 15, where the percentage desulfurization decreases when the concentration of dissolved oxygen falls below 1 part per million. The reason it is expected that as a result of incomplete oxidation reactions (H2SO3+ 1/2O2= H2SO4) if the small amount injected into the circulation tank 6 air, in liquid remains H2SO3, which slows down the absorption reaction (H2O+SO2=H2SO3). Thus, it is preferable to control the amount of oxidizing air to maintain in the absorbing liquid of dissolved oxygen concentration greater than 1 part per million by determining this concentration.

Although in this example, the dissolved oxygen concentration in the absorbing liquid is determined from, such as block 23 neutralization and so on, if the absorbing liquid is oxidized.

If the required quality gypsum low or low concentration of limestone particles in the absorbing liquid separator 31 can be excluded and further it is possible to combine the block 23 neutralization and the separator 31 to provide these functions in hardware. As the separator can be used any equipment, which can be divided particles of plaster of Paris and water, such as a thickener, a centrifugal dehydrator, etc.

In the following examples 4 - 6 describes the installation of desulfurization with the essential features of the flow direction of exhaust gas or systems contacting exhaust gas and the absorbing liquid.

Example 4.

Fig. 16 shows the installation of desulphurization in accordance with the present invention, provided with a grid tower. It is shown in Fig. 16 installation of desulphurization is a modification of the installation shown in Fig. 1, in which the desulfurization process is the same as in the spray tower desulfurization in example 1, except that the absorption of SO2in the exhaust is through the grate 34 installed in the tower desulfurization, and napus 1 tower desulfurization of the installed on top of the intake pipe 2 and is removed from the installed in the lower part of the tower of the exhaust pipe 3. In this process, the absorbing liquid is pumped by means of pump 5 of the absorbing liquid is supplied in the form of drops on the top of the grid 34 through a lot of spray nozzles 4 or holes (not shown) on the tube for the spray nozzle 4, so the grid 34 is contact between the absorbing liquid and the exhaust gas A. Thus, SO2in the exhaust And selectively absorbed by the absorbing liquid to the formation of sulphurous acid.

Formed in this way absorb drops containing sulphurous acid, is collected in the circulation tank 6, and is contained in the absorbing liquid sulphurous acid is neutralized by the limestone through the limestone layer 19 to the formation of gypsum is similar to the process in example 1.

Example 5.

Fig. 17 shows used in this example according to the present invention the installation of desulphurization, in which exhaust gas is injected into the absorption liquid through the tube. In Fig. 17 equipment and parts, operating as shown in Fig. 1, are denoted by the same numbers, and their further description is omitted.

Coming out of the boiler exhaust gas And is introduced into the housing 1 barnsdale into the absorption liquid in keeping her tank 37, installed on the bottom of the housing 1 of the desulfurization tower, through wuauuu exhaust gas pipe 35 connected to the intake pipe 2, through which is made the contact gas - liquid between the absorbing liquid and the exhaust gas A.

Thus, SO2in the exhaust And selectively absorbed by the absorbing liquid in the reservoir 37 to the formation of sulphurous acid. When shaking the mixer 38 sulfurous acid is oxidized to sulfuric acid oxidizing air, which is blown into the absorption liquid in the tank 37 of the blower 8, and neutralized loaded into the reservoir 37 limestone layer 19 to the formation of gypsum. Limestone D is shaken in the tank 37 through the mixer 38. Part of the absorbing liquid in the tank 37 is provided for the collection of plaster made from the reservoir 37 issue 20 in the dehydrator 13 through the discharge pipe 11 of the gypsum by means of pump 39. Limestone D is fed into the tank 37 through the limestone feed pipe 12.

Although in the examples 4 and 5, the absorbing liquid is neutralized, respectively, in the circulation tank 6 and the reservoir 37, the block neutralization can be installed on the outside of the desulfurization tower as in example 2. For example, if p and then return to the desulfurization tower, as shown in Fig. 33.

Example 6.

Although in the examples 1-5 is used, the vertical design of the installation of desulphurization, in which exhaust gas is introduced from the bottom or top of the desulfurization tower and is removed from the top or the bottom, in the present invention is also effectively used is shown in Fig. 18 installation of flue gas desulfurization horizontal (transverse) type, in which the path of flow of the exhaust gas is made not in the vertical direction. In this example, the installation of desulphurization includes a housing 1 of the desulfurization tower, the inlet pipe 2 and an exhaust pipe 3, in which the spray nozzle 4 for absorbing fluid is installed in the intake pipe 2 for spraying the absorbing liquid in the exhaust to absorb it SO2not long thereafter , containing SO2absorbing liquid drops in installed on the bottom of the desulfurization tower circulation tank 6 for exposure of its oxidation. The exhaust pipe 3 equipped with traps 9, so as not to produce volatile moisture from the desulfurization tower.

Coming out of the boiler (not shown) of the exhaust gas And is introduced into the housing 1 tower desulfurization of installed on its top in usausa liquid, pumped by pump 5 of the absorbing liquid sprayed into the tower desulfurization through multiple spray nozzle 4, thereby the contact gas - liquid between the absorbing liquid and the exhaust gas A. Thus, SO2in the exhaust And selectively absorbed by the absorbing liquid to the formation of sulphurous acid. Educated in this way absorbing drops containing sulfurous acid, allow to fall on the collecting plate 14 installed on the circulation tank 6. Absorbing liquid falling on the collecting plate 14, is collected and fed to the bottom of the circulation tank 6 through the introduction tube 15. On the way sulfurous acid is oxidized oxidizing air blown from the blower 8, prior to the formation of sulphuric acid.

With the bottom of the introductory tube 15 is connected distribution tube 17, which is available in the absorbing liquid in the circulation tank 6 allows absorbing fluid to move up uniformly across its plane. Coming from the introduction tube 15 absorbing the fluid enters the pipe 16 and then enters the distributing tube 17. Distributing tube 17 has plenty distribution the entire bottom plane of the circulation tank 6 to create them upstream. Sulfuric acid and limestone react to the formation of gypsum in the limestone layer 19, which oijala in the absorbing liquid in the circulation tank 6. Neutralized in the limestone layer 19 absorbing liquid is pumped to the spray nozzles 4 by pump 5 absorbing fluid through the pull-down of a fluid-absorbing tube 10. After neutralization of part of the absorbing liquid is supplied to the dehydrator 13 for dehydration and collection of plaster With.

Horizontal absorption tower according to the present invention includes such tower in which the gas tract in the tower is not only in the horizontal direction, as shown in Fig. 18, but in a slightly inclined or non-vertical direction.

Example 7.

This example solves the problem, shown in the accompanying Fig. 9 example 2.

As the absorbing liquid is neutralized by limestone D in unit 23 neutralization in Fig. 9, the neutralization rate is reduced when the particles of gypsum deposited on the surface of the limestone particles and, accordingly, it is preferable that the surface of the limestone particles in the block 23 neutralization recovered liquid.

The content is abiemnom drying oven 26 (Fig. 12) or with a mixer 25 (Fig. 11), or by liquefaction of limestone in the liquid. Further, according shown in Fig. 9 the process of absorbing liquid in block 23 neutralization neutralized raw limestone D with a relatively large particle diameter, whereas the content of the limestone D sprayed through the spray nozzles 4 absorbing fluid is low. Therefore, the problem in example 2 is that the pH value of the absorbing drops falling into the desulfurization tower, decreases with increasing concentration of SO2intake install desulphurization, decreasing the percentage of desulfurization.

According to this example in the installation of desulfurization wet type, in which the absorbing liquid with a reduced pH of the neutralized solid obesityvisit substance, such as raw and roughly crushed limestone with relatively large diameters of the particles, performance efficiency and a high degree of desulfurization can be achieved even in the case when increasing the concentration of SO2on the issue of installation of desulphurization.

The process of installation of desulfurization according to this example is shown in Fig. 19, equipment and parts, the ore unlike shown in Fig. 9 is further provided with a pipe 41 for supplying carboxylic acid or its salts E (this example uses formic acid).

Coming out of the boiler exhaust gas And is introduced into the housing 1 of the desulfurization tower from the inlet pipe 2 and is removed from the exhaust pipe 3. In this process, the absorbing liquid is pumped by means of pump 5 of the absorbing liquid sprayed into the tower desulfurization through multiple spray nozzle 4, thereby the contact gas - liquid between the absorbing liquid and the exhaust gas A. Thus, SO2in the exhaust And selectively absorbed by the absorbing liquid to the formation of sulphurous acid (H2O+SO2= H2SO3). Educated in this way absorbing drops containing sulfurous acid, allow to fall into the circulation tank 6. Sulphurous acid is then oxidized in the circulation tank 6 to the formation of sulfuric acid according to the chemical formula

H2SO3+1/2O2= H2SO4= 2H++ SO42-< / BR>
According to the formula above, a chemical reaction, the concentration of hydrogen ions (H+in the water temporarily increases (i.e., the value of +are connected to each other according to the following formula chemical reaction that causes a decrease in the concentration of hydrogen ions in the water (or raise pH)

2HCOO-+ 2H+= 2HCOOH

Formed in this way absorption liquid containing formic acid, is pumped by pump 42 in block 23 neutralization, after which the reaction occurs HCOOH with limestone D (CaCO3before re-education HCOO-in block 23 neutralization according to the following chemical reaction formula

2HCOOH + CaCO3= 2HCOO-+ H2O + Ca2++ CO2< / BR>
When the concentration of Ca2+and SO42-water will exceed their uptake, With gypsum crystallizes according to the following chemical reaction formula

Ca2++SO42-+2H2O=CaSO42H2O + CO2< / BR>
Because gypsum is contained in the absorbing liquid, which is neutralized in the block 23 neutralization, both can be easily separated, since the diameter of the particles of gypsum is about 10-50 μm, and the diameter of the particles of limestone in the block 23 neutralize an average of about 10 mm in order to avoid discharge of untreated particles of limestone, it is possible, for example, to install a wire grid 23 neutralize the upper part of the absorbing liquid. However, the slit of the block 23 neutralization absorbing liquid contains not only the plaster, but sometimes a small amount of limestone and, if necessary, is fed into the separator 31 to separate gypsum and limestone D. Part preparirovanie thus absorbing fluid with a lower content of limestone is served then in the dehydrator 13 for collection of plaster, and the other part with a higher content of limestone is returned to the spray nozzles 4 for selective absorption of SO2. Limestone D is served in the block 23 neutralization through limestone feed pipe 12. The separator 31 may be eliminated, if the quality of the collected gypsum is of no importance.

According to this process, since the absorbing liquid is neutralized in the block 23 neutralization with limestone particles, the neutralization rate of limestone D will be reduced if the surface of the limestone particles are deposited particles of gypsum. Accordingly, the surface of the limestone particles in the block 23 neutralization preferably is recovered by the liquid. Containing limestone D absorption liquid should vzbaltyvaya slowly, but continuously, for example by drying furnace 26 (Fig. 12) or is the use shown in Fig. 19 installation of desulphurization this example checks were performed desulfurization. The concentration of SO2in the exhaust at the inlet of the desulfurization tower was 1000 ppm. Limestone (with an average particle diameter of 1 mm) pre-loaded in block 23 neutralization in equimolar amount in relation to the SO2in the exhaust, i.e., in the amount sufficient for desulfurization for five hours, and then fed back through the supply pipe 12 in the amount of 0.97 molar ratio corresponding to the SO2in the exhaust. The volume injected into the circulation tank 6 air was 30 times the volume of SO2in the exhaust A. Muravlensky sodium was supplied into the absorption liquid through the tube 41 submission carboxylic acid or a salt thereof, to achieve a given concentration in the liquid.

Fig. 20 shows the relationship between the ratio of gas-liquid (i.e., the ratio of the volume of the sprayed absorbing liquid to the exhaust gas, referred to hereinafter as G/G) and percentage desulphurization, when the absorbing fluid is changed concentration moravcikova sodium. At a constant ratio G/W percentage of desulfurization increases with increase of concentration under the same conditions as in example 7, except that the pH on the release unit 23 neutralization was regulated by the amount of limestone in the block 23 neutralization. Fig. 21 shows the relationship between the pH value and the percentage value of desulphurization, when the ratio G/W and the concentration moravcikova sodium permanent. Impact moravcikova sodium is slightly noticeable at pH values less than 3.2. The check moravcikova sodium and other carboxylates found that a higher percentage of desulfurization can be obtained by controlling the amount of limestone and speed of fluid flow in the block 23 neutralization to maintain the pH of the absorbing liquid in the production unit 23 at a higher value than the constant pKaacid dissociation filed carboxylates.

Although the block 23 neutralization in example 7 is installed outside of the desulfurization tower, dripping in the tower desulfurization absorbing fluid may be injected at the bottom of the circulation tank 6, is installed at the bottom of the absorption zone for the formation of the upward flow from the bottom of the limestone layer, as shown in Fig. 1 and 2 (example 1) to oiiate limestone particles in the absorbing liquid that soprovojdali in the upper part of the limestone layer 19 (Fig. 1, and so on) to obtain the desired concentration moravcikova sodium in the absorbing liquid. Next, muravlensky sodium can be fed into the absorption liquid in the introduction tube 15, as shown in Fig. 1 and 2. In the circulation tank 6 in the limestone layer 19 thus formed upward flow of the absorbing liquid, which is the hallmark of this example, because it is shown in Fig. 11 stirrer and required for its operation means and associated power, are not necessary.

Although this example uses a vertical installation design method in which exhaust gas is introduced from the bottom or top of the desulfurization tower and is removed from the top or the bottom, in the present invention is also effectively used is shown in Fig. 18 installation of flue gas desulfurization horizontal (transverse) type, in which the path of flow of the exhaust gas is made not in the vertical direction. In this case, you can set the receiver to supply carboxylic acid or a salt thereof into the absorption liquid in the upper layer of limestone particles (corresponding to the limestone layer 19 in Fig. 18) to get emesto does not require grinding, because used here as a matter of raw limestone, etc., is easily separated from the solid particles of the product, such as gypsum (usually average particle diameter of 20-100 μm), because of its rawness (average particle diameter 0.5 mm and more), contributes to improving the quality of desulfurization, because the block neutralization may be loaded with a large amount of this substance, and gives a solid product of high quality due to less contamination of the product particles (Fig. 40). In addition, the quality of the product is improved by the addition of carboxylates. Used here carboxylic acids and/or their salts include such acids as formic acid, acetic acid, etc. and/or their salts.

Example 9.

This example is an improvement installation example 1 shown in Fig. 1 and 2.

According to the manufacturing process, as shown in Fig.1, its distinctive feature is that it does not require any fine ground particles of limestone D, no power for grinding, and produced the plaster is of high quality. However, there is a problem in that, if the installation of desulphurization stops and then starts again, the quality of OBEs hours).

The process to install desulphurization of this example is shown in Fig. 22, on which the equipment and parts that work the same way as shown in Fig. 1, are denoted by the same numbers, and their further description is omitted. Installation of desulphurization of this example is equipped with the next meter 21 pH values to determine the pH value of the absorbing liquid in the distributing pipe 17. In this example, the damping fluid is able to circulate in the desulfurization tower even after the supply of exhaust gas from the boiler stopped and the installation of desulphurization is stopped when the indication of the pH value of 5.5 is supported through the meter 21 pH, installed in the distributing pipe 17.

In the installation according to this example was tested desulfurization using limestone with an average particle diameter of 2 mm Concentration of SO2in the exhaust at the inlet of the desulfurization tower was 1000 ppm.

The change in the quality of desulfurization in time shown by the solid line (a) in Fig. 23, and the absorbing liquid was able to circulate in the desulfurization tower even after the supply of exhaust gas from the boiler stun adelayda tube 17, was indicidual pH value of 5.5, and started again after 24 hours.

It is seen that even after the operation stop of the obtained stable quality desulfurization.

Comparative example 3.

When you use the same installation as in example 9, was tested quality desulfurization after the re-start. In this comparative example, the circulation of absorption liquid in the desulfurization tower was stopped immediately after stopped the flow of exhaust gas from the boiler. The change in the quality of desulfurization in time shown by a dotted line (b) in Fig. 23, and the work was started again after 24 hours. It is seen that the condition with lower percentage desulfurization lasts one hour or more after resume.

Example 10.

Check desulfurization was carried out using the same setup and conditions as in example 9, except that the concentration of SO2in the exhaust at the inlet of the desulfurization tower was 3000 ppm. The result shown by the solid line (a) in Fig. 24. It is seen that the stable quality of the product is obtained even after resume.

Comparative primerjalna example 3 except that the concentration of SO2in the exhaust at the inlet of the desulfurization tower was 3000 ppm. The obtained result is shown by a dotted line (b) in Fig. 24. It is seen that the condition with lower percentage desulfurization lasts two hours or more after resume.

The quality of the product was also tested under conditions other than those described above. The result confirmed that the higher the concentration of SO2in the exhaust at the inlet of the desulfurization tower, the longer is the recovery of the product after resume in conventional technology, while in examples 9 and 10 stable quality is obtained even after resume.

When it stops working used in example 1 (Fig. 1) install desulphurization remaining in absorbing fluid H2SO3and H2SO4react with the limestone in the neutralization during a stop operation according to the previously described formula (3) reaction or the following formula reaction

H2SO3+CaCO3=CaSO32H2O + CO2) neutralization.

Example 13.

In example 12, the layer height izvestno the tank 6 and is also blown into the air. On the other hand, it is possible to keep the height of the layer of limestone D in General about the same through block 31 neutralize installed independently from the body 1 of the tower and connected to the circulation tank 6 through the connecting tube 10, when shaking the limestone layer 19 in block 31 neutralization mixer 25 and the flow supplied from the circulation tank 6 absorbing fluid up from the bottom of the block 31 of neutralization, as shown in Fig. 28.

Example 14.

This example was used to install desulphurization of topoch gases shown in Fig. 1. However, as shown in Fig. 29 is a partial sectional bottom of the circulation tank 6, which includes a distribution tube 17, this unit is supplied then stretched down the vertical tube 49 connected with the distributing pipe 17, which is shown in Fig. 2 and 4, and having on each end of the distributing hole 18. Under each vertical tube 49 equipped with a conical reflecting plate 50 to the direction of the absorbing liquid discharged from the distributing holes 18. Due to the vertical velocity distribution of the absorbing liquid (speed increases in a downward direction) near Ragusa plate 50, even if the speed is decreased emitted from distributing holes 18 of the absorbing liquid, allowing the limestone particles are easily airaudi.

When used in the installation according to this example of limestone with an average particle diameter of 2 mm has been reviewed desulfurization. The concentration of SO2in the exhaust at the inlet of the desulfurization tower was 1000 ppm. The relationship between the angle X the conic reflective plate 50 to the plane of the bottom of the circulation tank 6 and a percentage desulfurization shown in Fig. 30. The angle X preferably falls within the range of 30-70oaccording to the percentage of desulfurization on the graph.

You can also set the vertical tube 49 in the distribution tube 17 stretched upwards, as shown in Fig. 31, on which the vertical tube 49 provided with a distribution hole 18 at its top and a conical reflecting plate 51 above it, which is installed upside down in relation to the shown in Fig. 29, to prevent the influx of limestone particles back into the distribution tube 17 and to provide a uniform flow of the absorbing liquid discharged from the distributing holes 18 in the zone Nate is 32.

Example 15.

Used in this example, the installation of desulphurization unit 23 neutralization installed independently from the circulation tank 6, in which the spray nozzles 4 circulates only part in it absorbing fluid, and the other part is circulated to the unit 23 neutralization, as shown in Fig. 33. In this case, it is possible to independently maintain and regulate each circulation system absorbing fluid to the unit 23 neutralization and to the spray nozzles 4. Accordingly, if one of these circulation systems fails, the other operating system can be used to continue the work as a whole. As described in examples 9 and 10, to control the pH value of the absorbing liquid in the zone of neutralization easy when the installation of desulphurization of flue gases is stopped. I.e., when after stopping the operation of flue gas desulfurization only block 23 neutralize some time runs continuously, this block 23 neutralization can easily stop after the meter 21 pH value indicates the pH value of 5.5 in the absorbing liquid in the production unit 23 neutralization. When the installation of desulphurization of flue gases begins to work, the pH value of the absorbing liquid in the block 23 neutralization significantly reduced.

Further, when the tube in which the absorption liquid is circulated through the wet cyclone (not shown) connected to the block 23 neutralization from the path of flow of the absorbing liquid, which is located directly in front of the dehydrator 13, limestone D with larger diameter particles can be assembled in block 23 neutralization without passing it through the dehydrator 13.

Example 16.

The process of desulfurization of this example is shown in Fig. 34. In this example, performed air line 54 for absorbing fluid, non-circulating line 10 to the spray nozzle 4, to connect the bottom of the circulation tank 6 and the circulation line 53. Air line 54 is used for the liquefaction of the limestone layer 19, when the installation of desulphurization starts to work, thanks to which the absorbing liquid is pumped from the pump 56 directly into the circulation tank 6 without passing through the spray nozzles 4. Because the limestone layer 19 hydrostatically compressed, until the installation of desulphurization stopped, higher pressure is required for the liquefaction layer 19, when the installation starts again. Loss of pressure required to pump the absorbing fluid to spray is egco oijala. When limestone D origin, the circulation line absorbing fluid is switched from the bypass line 54 on the circulation line 53 and the work can continue, for example, in accordance with the process described in example 1. According to this example, the limestone D in the absorbing liquid is separated by the separator 31, followed by dehydration of the absorbing liquid, which thus through the dehydrator 13 is separated limestone D, to collect gypsum With.

Example 17.

The present invention is applicable to the installation of desulphurization of flue gases, provided with outer tower oxidation, as shown in Fig. 35. This installation method has three towers, i.e. the tower to perform the cooling and dust removal from exhaust gas (not shown), the housing 1 of the desulfurization tower for spraying the absorbing liquid to react with

SO2in the exhaust and tower 57 oxidation for the oxidation semitecolo calcium formed in the housing 1 of the desulfurization tower. The essential reactions in the installation of desulphurization of flue gases, is supplied is shown in Fig. 35 outer tower oxidation, are the following. Process normal condition is B>2the exhaust gas And is absorbed by the absorbing liquid (the main component of water) in the housing 1 of the desulfurization tower to the formation of the H2SO3, which then reacts with the sulphur calcium (CaSO31/2H2O) contained in the absorbing liquid, prior to the formation of hyposulphite of calcium (Ca(HSO3)2). The hyposulphite of calcium reacts with the limestone in the area of neutralization during the operation of passing through the limestone layer 19 to the education semitecolo calcium. Formed in this way sanitarily calcium is returned to the spray nozzles 4 and reacts with H2SO3, formed by the absorption of SO2in the exhaust A. on the other hand, part semitecolo calcium supplied to the tank 56 where its pH is adjusted by adding sulfuric acid G when shaken by a mixer 58, and then is fed into the tower 57 oxidation. The tower 57 oxidation air is supplied, allowing sulfurous acid is oxidized to form gypsum (CaSO42H2O) according to the formulas of chemical reactions

(Reaction absorption)

H2O+SO2=H2SO3,

CaSO31/2H2O + H2SO3= Ca(HSO3)2+ 1/2H2O

R)

CaSO31/2H2O + 1/2O2+ 3/2H2O = CaSO42H2O

As the limestone layer 19 in the zone of neutralization may be loaded with a large amount of limestone, and limestone D is loaded in a quantity sufficient to provide about 20 hours of continuous operation. This amount of limestone applied to each of the above-described example. Accordingly, if the limestone D is loaded into the neutralization area all at once during the night, when the installation of desulphurization is stopped, do not need to submit limestone D in the daytime or save crusher for limestone, etc. at night. In particular, since the limestone is loaded when the installation of desulphurization is stopped, there is no need to take measures to prevent sediment wet limestone D in limestone feed pipe 12 of the housing 1 of the desulfurization tower simultaneously with the loading of limestone D.

In order to apply limestone D with a given diameter of the particles in the installation of flue gas desulfurization, his original pieces as raw material crushed by the crusher, such as jaw, hammer, roller crusher and so on, and transferred to the installation. However, this original limestone D' in the nome example uses the transfer system raw material, which crusher 61 placed near or location of the source of limestone D', or the body 1 of the desulfurization tower for connecting honey original limestone D' and the housing 1 of the tower by means of the belt conveyor, as shown in Fig. 37 and 38.

In Fig. 37 shows a supply system of raw material, in which the original limestone D' is fed to the hopper 59, and then to the crusher 61, along with the installation of desulphurization of flue gases through the belt conveyor 58 and after grinding is served from delivering limestone tube 62 in block 23 neutralization through the hopper 63 and the spout 65. In Fig. 38 shows another system of supply of raw material, in which the original limestone D' is fed into the hopper 59 and then to the crusher 61 located near the location of the source of limestone D', by means of the belt conveyor 58 and after grinding is served in the block 23 neutralization through the hopper 63 and the dispenser 65 is placed near the body 1 of the desulfurization tower. In any of the delivery systems are not required to enter crusher 61 one-to-one in accordance with the total number of buildings 1 tower desulfurization, but it is possible to install one crusher 61 for maintenance of many buildings 1 tower obesere the air traffic management by placing only one crusher 61 near the location of the source of limestone D'.

Although Fig. 37 and 38 show examples in which the block 23 neutralization is selected independently from the body 1 of the desulfurization tower, it is clear that the present invention is not limited to these examples. Exhaust gas And is absorbed thereby absorbing liquid in the housing 1 tower desulfurization absorbing fluid is then oxidized by air and finally plaster With going through the dehydrator 13.

The amount to be fed through the block 23 neutralization with limestone D is governed by the dispenser 65 or operation on-off crushers 61, and the particle size of the limestone is controlled by varying the speed of the crusher.

In the above examples, the limestone selectively left in the neutralization area depending on the difference in deposition rate, due to the difference in diameters of the particles of limestone D and plaster, but both components can be separated, for example, through the grid or use the difference in inertial force, etc.

Although most of the above examples represent a construction in which the exhaust gas And is introduced from the bottom or from the bottom of the housing 1 of the desulfurization tower and is discharged from its upper part, and the body of the tower desulfurization in which polloway regardless of the direction of flow of exhaust gas And or manner of contact between the exhaust gas and the absorbing liquid (such as absorbing unit with a damp wall system for ozonation exhaust gas in the absorbing liquid through immersed in her tube, and so on).

According to the present invention in the presence of the absorbing liquid Al and F are almost never affects the quality of the product is as described above.

Further, the crushing of solid obeserver substances is not necessary, because using such a substance, such as limestone with large diameter particles; gypsum particles (20-100 μm in the General case) can be easily separated from the solid obeserver substances due to the large diameter of its particles (greater than 0.5 mm, preferably more than 1 mm); the higher the quality of desulfurization can be obtained because of the increased volume of solid obeserver substances in the neutralization area; finally, the solid product is improved, because the solid obeserve substance is not mixed with particles of solid products, such as gypsum.

1. The method of wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is provided in the resistance of the absorbing liquid for which I absorbed this way, the oxide of sulfur, subjected to neutralization, characterized in that the solid obeserve substance selectively left in the neutralization area of the absorbing fluid and selectively removed from the said zone neutralizing absorbent liquid containing water as a main component, and the solid products formed by the oxide of sulfur.

2. The method of wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, characterized in that oxidizes absorbing liquid after absorbing the exhaust gas in it and neutralize oxidized thus absorbing liquid solid obesityvisit substance that selectively left in the neutralization area of the absorbing liquid is removed from the said zone neutralizing absorbent liquid containing water as a main component, and the solid products formed by the oxide of sulfur, and absorbing liquid containing water as a main component, repeatedly contact with waste gas the substances under item 1 or 2, characterized in that in the zone of neutralization prevents the coating particles of the reaction products of solid obeserver substances.

4. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 3, wherein forming the flow of the absorbing liquid from the bottom part of the neutralization zone to the upper part of, or together with the aforementioned flow of the absorbing liquid or otherwise form the flow of air or gas from the bottom zone to neutralize its upper part to prevent the coating particles of the reaction products of solid obeserver substances, and the absorbing liquid is neutralized.

5. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 3, characterized in that the neutralization area shaken from the inside to prevent the coating particles of the reaction products of solid obeserver substances.

6. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 1 or 2, characterized in that the neutralization area is divided into many branches to prevent the coating particles of the reaction products of a feed flue gas using solid obeserver substances under item 1 or 2, characterized in that the absorbing liquid serves carboxylic acid and/or its salt.

8. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 7, characterized in that either the amount of solid obeserver substances, or the flow rate of the absorbing fluid regulate in order to raise the pH of the absorbing liquid prior to absorption of sulfur oxide in the exhaust is higher than the constant pKathe dissociation of carboxylic acid.

9. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 1 or 2, characterized in that the neutralization area determine the concentration of dissolved oxygen in absorbing fluid to control the amount of air for oxylene absorbing fluid that absorbs sulfur oxide in the exhaust.

10. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 1 or 2, characterized in that the solid obesityvisit substance is limestone, and the reaction product is gypsum.

11. The method of wet-type desulfurization of flue gases using solid otic more than the diameter of the particles of the solid product formed by the reaction of neutralization.

12. The method of wet-type desulfurization of flue gases using solid obeserver substances under item 1 or 2, wherein performing the path of the vertical type for the flow of exhaust gas, in which exhaust gas is introduced from the bottom and leave the top part, or the exhaust gas is introduced from the top and discharged from the lower part or tract of horizontal type for the flow of exhaust gas, in which the exhaust gas flows not vertically.

13. Installation of a wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, after which the absorption liquid containing absorbed thus the sulfur oxide is subjected to neutralization, characterized in that it contains a neutralization area of the absorbing liquid, and which selectively leave solid obeserve substance and selectively output of a fluid-absorbing, soderjanka wet-type desulfurization of flue gases using solid obeserver substances, in which the exhaust gas produced from combustion equipment such as boilers, is brought into contact with an absorbing liquid to absorb the sulfur oxide from the exhaust gas in the absorbing liquid, characterized in that it contains the absorption zone for contact of the absorbing liquid with the exhaust gas to absorb sulfur oxide from the exhaust gas in the absorbing liquid, the oxidation zone to oxidize the absorbing liquid containing the absorbed thus the oxide of sulfur, the neutralization area to neutralize the aforementioned oxidized absorbing fluid obesityvisit substance, selective separation of solid obeserver substances and selective removal of the absorbing liquid, containing water as a main component and the solid products formed from oxides of sulphur, and the circulation channel absorbing fluid for supplying the absorbing liquid containing water as a main component and the solid products formed from oxides of sulphur.

15. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 14, characterized in that the absorbing area contains an area contacting the gas - fluid desulphurization of flue gases using solid obeserver substances under item 15, characterized in that the area of contact of the gas - liquid set the grid for shielding the gas - liquid between the exhaust gas and the absorbing liquid.

17. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the neutralization area installed pipe system ozonation for introducing exhaust gas into the absorption liquid.

18. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the neutralization area provides a means for preventing the coating particles of the reaction products of solid obeserver substances.

19. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 18, characterized in that the means for preventing the coating particles of the reaction products of solid obeserver substance containing a branched distributing the path of flow of the absorbing liquid, which ramifies throughout the bottom layer containing solid obeserve substance for jet formation pagliusi the path of flow of air or water, which forks to the left, together with those of the branched distributing tract absorbing fluid or independently, across the bottom part of the mentioned layer of solid obeserver substances for jet formation transferred to air or water distribution.

20. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 19, characterized in that the branched distributing the path of flow of the absorbing liquid contains a vertical tube, provided at its end distributing hole to eject the absorbing fluid up or down, and in the neutralization area opposite the above distributing holes installed the reflecting plate.

21. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 18, characterized in that the means for preventing the coating particles of the reaction products of solid obeserver substances in the neutralization area contains sbaltimore blade or scraper installed in neutralization or neutralization area contains the rotator.

22. Installation of a wet-type desulfurization furnace g is non substance is loaded into each of the many branches of the zone of neutralization.

23. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that provided by the feed area for feeding solid obeserver substances in the neutralization zone, and said zone is equipped with a flushing unit to prevent deposits on the surface of its walls solid obeserver substances.

24. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the solid obesityvisit substance is limestone, and the reaction product is gypsum.

25. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the solid obeserve substance has an average particle diameter of 0.5 mm or more.

26. Installation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the path of the vertical type for the flow of exhaust gas, in which exhaust gas is introduced from the bottom and is discharged from the upper part, or trabot the exhaust gas, in which exhaust gas flows not vertically.

27. The method of stopping operation of a wet-type desulfurization of flue gases using solid obeserver substances, characterized in that the installation of a wet-type flue gas desulfurization stop after detecting that the pH value of the absorbing liquid that has absorbed the sulfur oxide, rises above the given value, when the installation of a wet-type flue gas desulfurization under item 13 or 14 is stopped.

28. The method of stopping operation of a wet-type desulfurization of flue gases using solid obeserver substance p. 27, characterized in that the installation of a wet-type flue gas desulfurization stop when detected that the pH value of the absorbing liquid that has absorbed the sulfur oxide, above 4.0.

29. The method of operation of a wet-type desulfurization of flue gases using solid obeserver substances under item 13 or 14, characterized in that the solid obeserve substance in the zone of neutralization shaken for approximate alignment height solid obeserver substances throughout the area neutralize what about the matter under item 13 or 14 begins to work or during work.

30. The method of operation of a wet-type desulfurization of flue gases using solid obeserver substances under item 29, wherein the determined one or more than two values of pressure loss solid obeserver substances in the zone of neutralization, the time of mixing device, the specific gravity of the absorbing liquid and the viscosity of the absorbing fluid to determine the conditions of mixing solid obeserver substances, and when you see that the height of the layer of solid obeserver substances varies according to the area of neutralization, in the solid layer obeserver substance is blown into the absorbing liquid, gas or water, or a layer of solid obeserver substances shake mixing device.

Priority points:

28.02.95 - PP.1, 2, 7, 8, 10 - 18, 24 - 29;

11.05.94 - PP.3, 5, 9;

11.05.95 - PP.6, 22, 23, 30.

 

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