Method for cleaning of exhaust gases of gas-turbine plant and device for its realisation

FIELD: technological processes.

SUBSTANCE: method for cleaning of exhaust gases of gas-turbine plant (GTP) includes installation of thermocatalytic neutraliser (TCN) in gas flue of GTP with developed catalytic surface in the form of panels, total area of surfaces of which, located cocurrently to direction of exhaust gases motion, exceeds area of cross section of GTP gas flue, at that TCN is installed in vertical gas flue of GTP, and required total volume of TCN panels is defined using the following expression: vk=Be.g.·τ, where: vk - required total volume of TCN panels, m3; B e.g. - volume flow rate of exhaust gases, m3/s; τ - required time for contact of exhaust gases with developed catalytic surface of TCN based on necessary extent of GTP exhaust gases cleaning, s. Device is suggested for cleaning of gas-turbine plant (GTP) exhaust gases, which includes thermocatalytic neutralizer (TCN), which is arranged with the possibility of installation in GTP gas flue along direction of exhaust gases motion and which represents casing open on top and bottom, inside of which panels of TCN catalytic units are installed as inclined in respect to vertical axis of casing and gas flue of GTP and are serially connected between each other, converging in adjacent top and bottom ends. Panels are made on the basis of highly porous cell materials, at that panels of catalytic units of TCN are formed by frame with wing spars, in which holders are inbuilt with catalytic units.

EFFECT: reduction of hydraulic losses in thermocatalytic neutraliser and required volume of catalyst, increase of extent of exhaust gases cleaning, compactness and manufacturability of layout of device for cleaning of exhaust gases of gas-turbine plant.

12 cl, 3 tbl, 6 dwg

 

The invention relates to techniques for purification of combustion products from harmful environmental pollutants (NOxand by dry selective interaction. While oxides of nitrogen (NOx) must be restored to nitrogen, and carbon monoxide (CO) to oxidize to carbon dioxide (CO2).

Known technical solution selective cleaning of flue gases of thermal power plants (TPP) is the restoration of NOxammonia [1]. However, the sanitary consequences of the use of solutions of nitric acid and the complexity of hardware design purification unit complicate large-scale use of ammonia recovery method of oxides of nitrogen.

Known technical solution is the transmission of combustion products through your catalytic surfaces [2]. The catalysts for purification of exhaust gases must meet very stringent requirements: high activity, selectivity of the catalytic activity, high mechanical strength and thermal stability. The lack of specific engineering solutions for the selective catalytic purification of products of combustion caused large emissions of NOxand on the domestic TPP.

Known bulk and monolithic multi-component catalytic system containing the active metals on different but is itulah [3]. However, this known solution is far from industrial implementation due to the limited experimental data on the chemical kinetics of catalytic reactions and process recommendations on the cleaning unit.

Known technical solution that implements selective dry cleaning exhaust gases on a highly porous cellular material (ITEM)on a metal surface which is coated first substrate made of aluminum oxide, and then the platinum group metals (Pt, Rh) as the catalytically active layer. Such thermal Converter (TKN) in the form of blocks of sizes 70×70×30 mm was used for purification of automobile exhaust gases [4].

The exhaust gases of the gas turbine units (GTU) contain About2to 15-16%, and the use of such TKN for large volumes of gases GTU very problematic. The necessary experimental data on the optimal contact times flue gas and hydraulic characteristics TKN installing them in the flue gas duct of the gas turbine engine.

The objective of the proposed method and device is the reduction of emission of harmful environmental pollutants GTU.

The technical result - the reduction of hydraulic losses in TKN and the required volume of catalyst, increasing the degree of purification of exhaust gases, compact size, and manufacturability of the layout of the device, providing the realizatio method.

The problem is solved and the technical result is achieved by the fact that according to the proposed method of cleaning exhaust gases of gas turbine unit (GTU) is installed in the flue gas duct of the gas turbine thermal Converter (TKN) developed a catalytic surface in the form of panels, the total surface area which is located spotno the direction of movement of the exhaust gases exceeds the area of the orifice of the duct of the gas turbine, while the set TKN in a vertical gas duct of the gas turbine and the required total volume of panels TKN determined using the expression:

Vto=ug·τ,

where Vto- the required total volume of panels TKN, m3;

Inug- volumetric flow rate of exhaust gases, m3/s;

τ - the desired contact time of the exhaust gases with the developed catalytic surface TKN based on the required degree of purification of exhaust gases of the gas turbine, S.

Contributes to the achievement of a technical result that:

- required time τ contact of flue gas with the developed catalytic surface TKN based on the required degree of purification of exhaust gases of the gas turbine is equal to 0,012÷0.02 s;

- based on the required degree of purification of exhaust gases of gas turbines and provide the necessary hydraulic resistance TKN total surface area of TKN, whic is its spotno the direction of movement of the exhaust gases, choose in excess of 6÷12 times the area of the orifice of the duct of the gas turbine;

- the necessary hydraulic resistance TKN is equal to not more than 400 PA;

- installation of TKN in the vertical flue GTU perform in the direction of the flue gases after the location of the heat exchanger in the zone of the flue gas temperature 380÷450°C;

- bring the degree of purification of exhaust gases of the gas turbine to values: NO2- 100%, NO - 50-60% and 80-90%.

In relation to the object of the invention is a device - technical result is achieved in that the device cleaning of flue gases of gas turbine unit (GTU) includes thermal Converter (TKN), made with the possibility of installation in the flue gas duct of the gas turbine in the direction of travel of exhaust gases and being an open top and bottom casing, inside of which is inclined relative to the vertical axis of the casing and flue GTU placed sequentially interconnected converging in the adjacent top and bottom panels catalytic converters TKN, made on the basis of a highly porous cellular materials, and panel catalytic converters TKN formed by a frame with side members which are mounted clip with catalytic units.

Contributes to the achievement of a technical result that:

- TKN made in the form of a separate removable with the work;

- the height of a separate removable section TKN does not exceed the height of the body;

the housing top and bottom perimeter has an external mounting flanges, adapted for the installation of the sealing elements, resistant to high temperatures, and for fixing the fastening elements in the flue gas duct of the gas turbine;

on the surface of the panels catalytic converters TKN, made on the basis of a highly porous cellular materials, applied as catalyst film of rare metals;

- side ends of the panels, catalytic converters TKN and lower ends of the outer panels catalytic converters TKN tightly abut the walls of the shell.

Figure 1 shows the design of the gas turbine installation (GTES-2,5) with flue and device cleaning of flue gases of the gas turbine; figure 2 shows the device cleaning of flue gases of the gas turbine; figure 3 shows a panel TKN; figure 4 - scheme of fastening TKN in the device cleaning of flue gases of the gas turbine; figure 5 shows a longitudinal section of the device cleaning of flue gases of the gas turbine; figure 6 is a top view of figure 5.

The method of purification of exhaust gases of gas turbine unit (GTU) is as follows.

In the gas duct 1 GTU in the direction of travel of exhaust gases are mounted device 2 cleaning of flue gases of the gas turbine, representing fixed in the housing 3 TKN advanced catalic the cooling surface in the form of panels 4, the total surface area which is located spotno the direction of movement of the exhaust gases exceeds the area of the orifice of the duct 1.

The housing 3 is open at the top and bottom. Inside the housing 3 inclined relative to the vertical axis and the axis of the duct 1 are placed sequentially interconnected converging in the adjacent upper and lower ends 5 of the panel 4.

Case 3 at the top and bottom perimeter has an external mounting flange 6, adapted for the installation of the sealing elements (not shown), are resistant to high temperatures, and for fixing the fastening elements (not shown) through the holes 7 in the duct 1 to its mating flanges. TKN made in the form of a separate removable section. The height of a separate removable section TKN does not exceed the height of the housing 3. Panel 4 consist of catalytic converters 8, made on the basis of a highly porous cellular materials coated with a catalyst film of rare metals. The lateral ends of the panels 4 catalytic converters 8 TKN and lower ends of the outer panels catalytic converters TKN tightly abut the walls of the shell.

Panel 4 catalytic converters TKN have the 9 cell and is formed by a frame 10 with the side members 11. The frame 10 is mounted cage with catalytic blocks 8.

Catalytic blocks 8 with clips, I laid in the side 9 of the frame 10. This section of the panel 4 catalytic converters 8, for example, the area of Spthat is the basis for TKN. In our case, the frame 10 sections stacked 40 catalytic converters 8.

Catalytic panels 4 are set obliquely to each other, and the ends are fixed by the fastening elements 12.

In relation to GTES-2,5 flue 1 is a cross-sectional area Sg(the amount in section 1690×1690 mm). The housing 3 of the device 2 cleaning of flue gases of the gas turbine has a height of 1000 mm, Such thermal "spacer" is mounted in the duct 1 GTU after heat exchanger (not shown), i.e. in the temperature range 380-450°C.

The device 2 cleaning of flue gases of the gas turbine manufactured for experimental verification of the effectiveness of the proposed method when cleaning exhaust gases from the NOxand on GTES-2,5. Catalytic blocks 8 having dimensions 170×100×20 mm, with clips inserted into the cells 9 of the frame 10. Based on the gathered section of the panel 4 square Spcan be mounted TKN different geometric sizes (depending on the cross-section of the flue GTU).

Due to the inclined arrangement of series-connected between a converging adjacent the upper and lower ends of the 5 panels 4 and securing them to the ends between the fastening elements 12 can collect TKN developed with a single catalytic surface is firm. While the total hydraulic resistance TKN does not exceed 30-40 mm Vogt (300-400 PA).

The contact time of the exhaust gases with the developed catalytic surface TKN coated with a catalyst film of rare metals (Pt And 80%Rh - 20%) is sufficient for full recovery NO2(NO2+CO→NO+CO2) and partial (60%) NO (2NO+2CO→N2+2CO2). Oxidation is provided WITH 80-90% excess oxygen in the flue products (2SD+O2→2CO2).

The optimal temperature flow catalytic reactions of reduction of nitrogen oxides is an interval 380-450°With, so the machine cleaning of flue gases is installed in the flue gas duct of the gas turbine after the heat exchanger. It should be noted that the oxidation of CO flue gas temperature increases.

Industrial applicability of the proposed method is conrmed by the optimization experiments.

The experiment was carried out at an operating gas turbine (grabinski, NPO "Saturn")designed to generate electricity for own needs (GTES-2.5 and 2.5 MW). During these activities it was necessary to find technical and constructive solutions TKN, satisfying the following options:

hydraulic resistance TKN should not exceed 300-400 PA;

- stepenosky exhaust gases from the NO xand must be at least 40-60%.

This inconsistency of these requirements is that the contact time of the exhaust gases with a catalytic surface, sufficient for the reactions of recovery NOxand CO oxidation, leads to a developed surface TKN, as required in connection with this increase in surface TKN can lead to growth of its hydraulic resistance (when in serial catalytic panels).

Therefore, the main objective of the conducted research poster on GTES-2,5 was to find the optimal structural and technological solutions that satisfy the above requirements.

Table 1 summarizes the data on the six variants of designs TKN. In the first two variants TKN catalytic surface panels disposed normal to the flow of exhaust gases STU: in the first variant - two panels, the second variant - 4 panel. In the first variant - small time leaving flue gases, and therefore, an extremely small degree of purification from NO. In the second variant, increased contact time and simultaneously increased hydraulic resistance TKN.

Therefore, in the second series of experiments (range 3-6) catalytic panels were located spotno stream leaving flue gases.

The most compact and technology the primary linking device, ensuring implementation of the method and meets the desired parameters on hydraulic resistance (not more than 400 PA) and contact time on the catalytic surface TKN (not less than 0,012), are inclined panel design (5th and 6th editions). However, preference should be given to the 5th option, because in the 6th embodiment, a metal partition between the parallel panels not only increase the intensity TKN, but susceptible to thermal deformation.

Table 1.
The main parameters of designs TKN
Design TKNThe total hydraulic resistanceThe residence time of flue gas in TKN,Note (required parameters)
PAmm Vogt
TNK has normal flow1. Panel 2400400,0014Insufficient contact time
2. Panel 412001200,0043Insufficient contact time, high hydraulic resistance
T is To set spotno stream 3. A single glass in the flue100100,0043Insufficient contact time
Thakyou on the diameter of the flue 16300-35030-350,014Structural complexity
5. Panel sloping353,50,0176Satisfies both
6. Panel parallel35-403,5-4,00,0176Satisfies both of the parameters, but excessive metal

Thus, the total hydraulic resistance of the 5-th and 6-th of designs TKN is not more than 40 PA (4 mm waters. century), and the contact time of leaving flue gases to the catalytic surface is 0,017-0,018 with that 45-50% more than in the automotive Converter [4].

Hence, the claimed invention was based on the design of the TKN in the fifth variant (Figure 2).

While table 2 shows the experimental data on the purification of exhaust gases, depending on the amount (volume) dialed in TKN catalytic panels.

Table 2.
The degree of purification
№ p/p The number of panelsHydraulic resistance, PAThe time of contact withThe degree of purification, %Note
NOCO
1234567
1812600,00831,063,0Does not meet on hydraulic resistance and purification
2124000,01248,074,0Meets on hydraulic resistance and purification
3163500,017655,085,0
4202200,0264,091,0
5241850,0471,095,0Meets on hydraulic resistance and degree of purification, but the high cost of TKN

The number dialed panels in TKN ranged from 8 to 24. However, only in the case of the composition of TKN 12, 16, 20 and 24 panels (experiments 2, 3, 4, and 5) the hydraulic resistance and power of the ü cleaning of flue gases meet the required parameters.

In the fifth variant (24 panels) high cost of catalytic panels (more than 4% of the value of GTU)which does not meet the cost requirements of manufacturers and consumers GTU.

Therefore, the optimum contact time is defined in the present invention the size of 0,012-0,02 C.

In relation to GTES-2,5 was determined required amount of catalytic panels:

vk=Bug·τ=30,77 m3/s · 0,016 = 0,492 m3

The weight flow rate of exhaust gases in operating mode (2.5 MW) was equal to 16 kg/s, while their specific weight of 0.52 kg/m3volumetric flow rate of exhaust gases is:

.

The required contact time selected medium in the recommended interval 0,012-0,02, i.e. τ=0,016 C.

Catalytic panels had size: 1,69×1,0×0.02 m, i.e. the volume of one panel is equal 0,0338 m3.

Therefore, the required required optimal total volume of panels TKN is in 15-16 panels:

0,492:0,0338≈15 panels

In the experiment TKN (GTES-2,5) contained 16 catalytic panels.

Depending on the number of catalytic panels (12-24) the ratio of the total surface area TKN located spotno the direction of travel of exhaust gases SΣpto the area of Sgorifice of the duct of the gas turbine is in the range of 6÷12, i.e. observed soo is wearing:

SΣp·k/Sg=6÷12,

where: SΣp- the total surface area of TKN, located spotno the direction of movement of the exhaust gases, m2;

Sg- area flow area of the flue GTU, m2;

k - coefficient taking into account the decrease in the real surface area TKN due to the presence in the panel frame, frame rails, clamps (k=0,85).

SΣp·k/Sg=1,69·1,0·12·0,85/1,69·1,69=6 (12 panels)

SΣp·k/Sg=1,69·1,0·24·0,85/1,69·1,69=12 (24 panels)

Table 3 shows the composition of exhaust gases GTES-2.5 operating modes of GTP without installation in duct cleaning exhaust gases of gas turbines and installing it, and cleaner exhaust gases includes 16 catalytic panels TKN.

Table 3.
The composition of the exhaust gases GTES-2,5
№ p/pPower, kWConcentration, mg/m3
N2NONO2COCO2O2CH4
123456 789
127001024493,313,985,3175,047142,1235710,4857,1
1024522,86,26026,2549732,9232260,30
223001007973,57,545,9287,541249,3244281,7964,3
1007989,43,37043,1244285,1240319,10
318501003847,35,131,2575,035356,6252853,01021,4
1003858,1to 2.29086,2538933,5248511,20
41450998327,44,024,6825,031428,1261424,31178,6
998335,91,800123,7535771,0256327,70

Note. When the characteristic of the concentration of substances in the numerator bring the us concentration on operating modes (without installation in the flue GTU device cleaning of flue gases), and the denominator of the concentration after the installation of the proposed device cleaning of flue gases in the flue gas duct of the gas turbine engine.

The degree of purification of exhaust gases from the NO2was 100%, NO - 50-60% and 80-90%.

Thus, implementation of the proposed invention leads to a significant purification of exhaust gases of the gas turbine. Plans to make broad use of the developed method in a maintained Park GTU and manufacturing plants, gas turbine plants, which will lead to environmental improvement of the atmosphere.

The application of the invention it is possible in other fuel combustion devices.

The proposed device cleaning of flue gases is intended to equip them GTU as manufacturing plants, and operating on objects (pumping units) OAO "Gazprom". Currently, a program of their making and implementation at industrial facilities.

Sources of information

1. Noskov A.S., and other Technological methods of protection of the atmosphere from emissions of energy sector companies. Novosibirsk: SB RAS, science and technology, 1996, s.

2. Kuzmin RI and other Catalytic treatment of gaseous emissions of oxides of nitrogen and carbon // Russian chemical journal. - 2000. No. 1. - p.71-76.

3. Patents of the Russian Federation No. 2054959, 1996; No. 2062140, 1996.

4. Patents of the Russian Federation№2107171, 1998; №2163673, 2001; №2163674, 2001.

1. The method of purification of exhaust gases (the country : Russia the second setup (STU), including installation in the flue gas duct of the gas turbine thermal Converter (TKN) developed a catalytic surface in the form of panels, the total surface area which is located spotno the direction of movement of the exhaust gases exceeds the area of the orifice of the duct of the gas turbine, while the set TKN in a vertical gas duct of the gas turbine and the required total volume of panels TKN determined using the expression:

vk=Bug·τ,

where vk- the required total volume of panels TKN, m3;

Inug- volumetric flow rate of exhaust gases, m3/s;

τ - the desired contact time of the exhaust gases with the developed catalytic surface TKN, based on the required degree of purification of exhaust gases of the gas turbine, S.

2. The method according to claim 1, characterized in that the required time τ contact of flue gas with the developed catalytic surface TKN, based on the required degree of purification of exhaust gases of the gas turbine is equal to 0,012-0,02 C.

3. The method according to claim 1, characterized in that, based on the required degree of purification of exhaust gases of gas turbines and provide the necessary hydraulic resistance TKN, total surface area TKN located spotno the direction of movement of the exhaust gases, choose greater than 6 to 12 times the area of the orifice of the duct of the gas turbine engine.

. The method according to claim 3, characterized in that the required hydraulic resistance TKN is equal to not more than 400 PA.

5. The method according to claim 1, characterized in that the installation of TKN in the vertical flue GTU perform in the direction of the flue gases after the location of the heat exchanger in the zone of the flue gas temperature 380÷450°C.

6. The method according to claim 1, characterized in that the adjusted degree of purification of exhaust gases of the gas turbine to values: NO2100%, NO 50-60% and 80-90%.

7. Device cleaning of flue gases of gas turbine unit (GTU), including thermal Converter (TKN), made with the possibility of installation in the flue gas duct of the gas turbine in the direction of travel of exhaust gases and being an open top and bottom casing, inside of which is inclined relative to the vertical axis of the casing and flue GTU placed sequentially interconnected converging in the adjacent top and bottom panels catalytic converters TKN, made on the basis of a highly porous cellular materials, and panel catalytic converters TKN formed by a frame with side members which are mounted cage with catalytic units.

8. The device according to claim 7, characterized in that TKN is made as a separate removable section.

9. The device according to claim 8, characterized in that the height of a separate removable section TC does not exceed the height of the tank.

10. The device according to claim 7, characterized in that the housing top and bottom perimeter has an external mounting flanges, adapted for the installation of the sealing elements, resistant to high temperatures, and for fixing the fastening elements in the flue gas duct of the gas turbine engine.

11. The device according to claim 7, characterized in that on the surface of the panels catalytic converters TKN, made on the basis of a highly porous cellular materials, applied as catalyst film of rare metals.

12. Device according to one of claims 7 to 11, characterized in that the lateral ends of the panels, catalytic converters TKN and lower ends of the outer panels catalytic converters TKN tightly abut the walls of the shell.



 

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FIELD: chemical industry; methods of neutralization and a utilization of the aggressive chemical compounds.

SUBSTANCE: the invention is pertaining to the field of neutralization and a utilization of the aggressive chemical compounds, in particular, the saturated with the anhydrides acid-containing compounds and wastes. The neutralization is applied to the smoke mixture containing the sulfuric anhydride and chlorosulfonic acid, or the oxidizing agent of the rocket propellant based on of the nitric acid containing a dimer of the nitrogen dioxide. For neutralization use the hydrolyzed dispersible aluminosilicates based of the natural clays selected from: hydromicaceous Cambrian clay, montmorillonite clay, kaolinite clay or on the basis of their mixtures. At that the hydrolyzed dispersible aluminosilicates, which are taken at least in equal shares with an aggressive chemical compound, are prepared at the following ratio of components (in mass shares): a dry substance - 1.0-2.5, water - 1.0. The invention allows to neutralize the aggressive wastes and to produce the useful product with the sorption activity.

EFFECT: the invention ensures neutralization of the aggressive wastes and production of the useful product with the sorption activity.

3 cl, 2 ex, 6 tbl

FIELD: complex cleaning of various industrial gaseous emissions.

SUBSTANCE: proposed method may used for complete entrapping of toxic gases, such as NOx, SO2 and CO from flue gases of fuel burning units and gaseous emissions from production units. Proposed method includes pumping of gas flow to be cleaned through reservoir filled with reaction fluid followed by settling, separation of reaction products in form of sediment and their utilization. Used as reaction fluid is trifluoroacetic acid saturated with oxygen. In the course of cleaning, composition of cleaned gases is monitored continuously. In case of penetration of contaminants, flow of gases being cleaned is directed to second reservoir filled with new portion of trifluoroacetic acid saturated with oxygen. Used trifluoroacetic acid is regenerated by saturating it with oxygen and is directed to re-cycle.

EFFECT: efficiency close to 100%.

1 ex

FIELD: catalyst for improved hydrolysis of carbon oxysulfide (COS) and hydrocyanic acid (HCN) in gaseous mixtures.

SUBSTANCE: invention relates to application of TiO2-based composition as catalyst for COS and/or HCN in gaseous mixture releasing from apparatus for joint energy production, wherein said composition contains H2, CO, H2S and H2O in amounts of 10-40 %; 15-70 %; 200 ppm-3 % and 0.5-25 %, respectively. Moreover abovementioned composition contains at leas 1 mass.%, preferably at least 5 % at least one alkali-earth metal sulfate selected form calcium, barium. Strontium, and magnesium.

EFFECT: high conversion ratio of COS and HCN, irresponsiveness to presence of NH3, decreased production of CO2 and CH4.

8 cl, 5 ex

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