Ozone Robot Environmental Equipment Ltd The introduction of

Ozone Robot Environmental Equipment Ltd The introduction of ozone oxidation The technology of advanced flue gas denitrification

01 The emission standard of flue gas and treatment status

Ultra low emission standard for flue gas The pollution control of SO 2 and NOx in coal-fired flue gas is the most task in air pollution control at present. Ultra low emission standard：the emission concentration of boiler flue gas pollutants from thermal power plant reach the Emission Standard of Gas Turbine through high removal. standards Gas and dust mg/Nm 3 SO 2 mg/Nm 3 NOX mg/Nm 3 GB 13223 -2011 30 Special emission limit 20 50 100 The action plan for upgrading and renovation of coal and electricity energy conservation and emission reduction. 10(5) 35 50 USA 20 184 135 European Union 30 200 Common requests New boiler： 100 existing： 200 100 《Emission Standard of air pollutants for thermal power plants GB 13223 -2011》 Standard leap Renovation of technology 《 Emission Standard of air pollutants for thermal power plants GB 132232011》

The treatment status of flue gas The coal as main energy sources emits a lot of pollutants such as SO 2、 NOx and others during the combustion process that will cause serious air pollution and endanger human health. Control NOx in coal combustion Low oxygen combustion method, two stage combustion method and flue gas recirculation method and others are relatively economical, but the efficiency of emission reduction is low and can’t meet the requests of environmental protection. Physicochemical removal Catalysis, absorption, discharge and others. the selective catalytic reduction(SCR) is widely used.

02 The denitrification technology comparison for rear flue gas

The comparison of dentrification principle SCR Select proper catalysts, the reaction temperature is SNCR When the flue gas decreased to suitable temperature is 850～ 950 range(300～ 420 ℃) , the ℃, spray the reducing agents(liquid agents including liquid ammonia, urea and others) ammonia, urea and selectively react with NOx others into flue gas to in flue gas to reach react with NOx and denitrification effect. produce nitrogen and water. Ozone denitrification To oxidize the insoluble low-valent nitrogen oxides to high-valent soluble nitrogen oxides using strong oxidants, then the high-valent nitrogen oxides will be removed by alkaline absorbents.

The comparison of application features SCR l l It is one of the most widely SNCR l Denitrification for applied and mature flue small boiler and gas denitrification circulating fluidized technologies in the world. bed boiler. It is one of NOx pollution controlling method applied in large coal-fired power plants in China. Ozone denitrification l Combined with other l The high and unstable NOx emission concentration in petroleum and chemical industries and others. l The high NOx emission denitrification concentration and much technology. dust in glass and cements kilns and others

The comparison of advantages and disadvantages by individual application SCR advant ages disadva ntages The removal rate can reach 85%; mature technology and easy handling. High cost on construction, operation and catalysts. The catalysts losing effect are dangerous wastes. Unstable operation, inconvenient maintenance. There are safety problems in storage and operation of liquid ammonia. SNCR Small site area and investment The NOx removal rate can only reach 30%～ 50% in large boiler, needs to increase the flue gas temperature. 臭氧 脱硝 It doesn’t need to increase the flue gas temperature, no reducing agents such as ammonia added. When the NOx and flue gas content are not stable, the removal rate can keep over 90%. Meanwhile treat heavy metals；then can reach the desulfurization effect. The application cases are less than SNCR and SCR，the equipment investment and usage cost are higher when the total NOx content is high.

Comparison of technic process SCR SNCR Ozone oxidation

The technology advantages of denitrification by ozone Suitable for kinds of flue gas treatment Remove many kinds of pollutions at one time Flue gas of boiler, wastes combustion, cement kilns, glass kilns, sintering machine and other flue gas Simple renovation, save area oxide and absorb the pollutants such as NO and Hg and others, reach the goal of simultaneous multi -pollutants removal. 06 01 05 High removal rate： Take the ozone to the flue gas pipe in front of desulfurization tower, no construction. The recycled sources by multipollutant removal The nitrite and nitrate products treated by multi-pollutant removal are potential resources, can have the comprehensive utilization of sulfur and nitrogen The rate of desulfurization and 02 04 03 denitrification can reach over 90%. Save cost Ozone oxidation is selective and can adjust according to the pollutants concentration in flue gas to reduce unnecessary consumption.

The choice of denitrification technology The single traditional SCR and SNCR can’t meet the emission requests, ozone technology must be added to control the pollution emission, the new combined process attract much attention. Step 1 SNCR/SCR＋ ozone Using traditional and low cost process to remove NOx in front of process to decrease the concentration initially. Step 2 Ensure NOx concentration to meet the national emission standard using advanced ozone oxidation process.

03 The reaction principle of flue gas denitrification by ozone oxidation

The brief introduction of ozone The gas state is blue, the liquid is dark blue, the solid is dark-purple. The ozone 01 is easily decomposed to oxygen and oxygen atoms in normal temperature. So Ozone features it needs to make and produce on spot. Ozone is a high efficiency and clean strong oxidant, the sterilization ability is stronger than chlorine, no secondary Ozone preparation pollution. With the development and perfecting of ozone generation and 02 Ozone application 03 The methods of ozone generation include ultraviolet method, electrolytic process, radiation method、spark discharge, corona advanced oxidation discharge and others, corona technology, it is commonly discharge is the most feasible applied in flue gas treatment. method so far.

The reaction principle of flue gas denitrification by ozone oxidation oxidants Oxidation potential(V) The ratio with chlorine 0 H- 2. 80 2. 05 O 3 2. 07 1. 52 H 2 O 2 1. 78 1. 31 1. 70 1. 25 Na. CIO 1. 49 1. 10 chlorine 1. 36 1. 00 Chloride 1. 27 0. 93 oxygen 1. 23 0. 90 KMn. O 4

The reaction principle of flue gas denitrification by ozone oxidation The main component of NOx in flue gas is NO (95%). Ozone can oxidize water-insoluble NO to water-soluble NO 2, N 2 O 3, N 2 O 5 and other high-valent nitrogen oxides. Then convert the NOx to calcium nitrate and calcium sulfate by alkali absorption. OPTION = NO 2 + O 2 2 NO 2 + O 3 = N 2 O 5 + O 2 formula Main reaction NO + O 3 NO 2 + O 3 = O 2 + NO 3 2 NO +3 O 3 =N 2 O 5 +3 O 2 NO 2 + NO 3= N 2 O 5

The reaction principle of flue gas denitrification by ozone oxidation Calculation of ozone dosage n(O 3)/n(NO)=1. 1 m(NO)=0. 62×m(NOx) （Nox concentration is calculated as NO 2） M(O 3) ≈1. 1×Q×∆m(NOx)

The denitrification principle of ozone oxidation and its selectivity. Reaction formula NO + O 3 — NO 2 + O 2 2 NO 2 + O 3 — N 2 O 5 + O 2 Relative reaction speed 62780 135 very fast Fast SO 2 + O 3 — SO 3 + O 2 8 low CO + O 3 — CO 2 + O 2 1 Very low The relative reaction rate sheet of flue gas components by ozone oxidation Selectivity: Compared with other components in flue gas, ozone has a very high selectivity to the oxidation reaction of NOx, which is rapidly converted into water-soluble substances, and these compounds are easily absorbed by water washing.

The solubility of products oxidized by ozone substances the solubility of 25℃ NO 0. 063 NO 2 1. 26 SO 2 126 N 2 O 5 HNO 3 >126 Infinitely dissolve with water(mg/l) the solubility sheet of nitrogen oxides, sulfur oxides of glue gas in water Solubility: It can be seen that NO oxidized into NO 2 and N 2 O 5 is easily soluble in water and is conducive to be absorbed by desulfurized slurry.

The denitrification principle of ozone oxi NO oxidized into NO 2 and N 2 O 5 is easily soluble in water and is conducive to be absorbed by desulfurized slurry.

04 The technology of flue gas denitrification by ozone oxidation

The general process drawing Process water tank Booster fan of desulfur ization Reaction tower of denitrificat ion and desulfuriza tion Compound absorbents tank Process water Bag deduster Sintering machine Electric deduster Desulf urizatio n residue catalyst Sintering fan Back-flow control valve chi mne y

The system of flue gas denitrification by ozone oxidation—process drawing The ozone sterilization system mainly include air source system, ozone generator, cooling water system, electric and control system, ozone spraying system and NOx absorption system. air source system cooling water system ozone generator spraying gas system Absorption system control system

The system of flue gas denitrification by ozone oxidation—process composition The system of flue gas denitrification by ozone oxidation Ozone generation system Flue gas system chimney Anticorrosion and drainage Expansion joint Metal expansion joint Gas-gas mixer Ozone generator Cooling water system Oxygen sources Absorption system Absorption tower of desulfurizati on Byproducts treatment desilter Electrical equipment control Drainage pump Control system

Ozone Robot plate type ozone generator The operating cost of the ozone generation System independently developed by our company is low, and the energy consumption per kilogram of ozone operation is about 7 kw/h. principle： the insulating dielectric layer between two parallel electrodes keeps the discharge gap. When high voltage current is applied, an alternating high-voltage current will be generated. When air or oxygen passes through the discharge gap, the oxygen molecules are aroused by high energy electrons and get energy, then collide with each other to form ozone molecules.

Ozone Robot plate type ozone generator The principle of Ozone Robot ozone generator：generate ozone according to dielectric barrier discharge High voltage electrode Dielectric——ceramics、glass、enamel energy O 2 O 3 heat Cooling water Ground electrode Oxygen molecule O 2 Free oxygen atom O and oxygen molecule O 2 (high voltage) 3 O 2==== 2 O 3 Ozone mixture O 3

The process drawing of VPSA oxygen generator 01 Oxygen or gas containing oxygen, try best not to contain prohibitive materials such as moisture, dust, oil, hydrogen and hydrocarbons. 02 Oxygen generator requires that the pressure is 0. 1 -0. 15 Mpa, the dew point is -60℃ calculated as 8 m 3 ozone per kg.

The requests of cooling water quality name performance parameter The consumption of internal circulation cooling water（t/h） 2 xx Internal The pressure of internal circulation cooling water(Mpa) 0. 1 -0. 15 circulation The inlet water temperature of internal circulation cooling water(max. C) The outlet water temperature of internal circulation cooling water( C) <33 note Meet the quality requirement of salt water <35 The consumption of rated external cooling water（t/h） 2. 4 xx circulation Supply water pressure（MPa） 0. 2 -0. 3 cooling Supply water temperature（max. C） ≤ 30 system Return water temperature（ C） 33 External Ozone generator The supply water pressure of entering plate type heat exchanger

The system of spraying oxygen To mix ozone with NOx in flue gas completely, the ozone produced will be sent to the flue gas pipe for treatment through grille device of spraying oxygen. Oxide the NO to NO 2，which will be absorbed by rear absorption tower picture：the grille device of spraying oxygen and gas-gas mixer in reactor

Absorption system The glue gas spraying liquid with NO 2 and SO 2 Desulfurization tower Absorption tower（ old one） The residual Ca(NO 2)2 /Ca(NO 3)2 will continue to react Absorption reaction absorbents: Ca. CO 3 slurry Sulfate, nitrite soluble Desulfurizat ion slurry Ca. S 03 By oxidation air Ca. SO 4 · 2 H 2 O Rear dehydration system Remove gypsum Small part wastes solution Open sedimentation supernat ant Waste water treatment system Sedimentation or crystallization Grab cart The grille of spraying oxygen and rear chimney needs to have high temperature scale coating for ozone’s strong corrosiveness. The absorption tower also needs part renovation.

Absorption process of desulfurization and denitrification.

处理效果 Ind ust ria l te st on -sp ot flue gas denitrification is completed at 150 ℃ and below temperature. The desulfurization efficiency is higher than 95%, the denitrification efficiency is higher than 80%, and the dust emission concentration is less than 5 mg/m 3.

The features of Ozone Robot ozone generator system High safety 01 Non-pressure vessel, no explosion risk Low purchasing and maintenance No-spare whole equipment, durable maintenance. Container type 07 02 Good stability The concentration and output of ozone will not decay 06 03 Quick installation and maintenance on spot. High concentration Ozone concentration can reach over 200 mg/l. Low operation cost The rated power consumption of ozone engine with 1 kg. O 3/h is ≦ 7. 0 kwh 04 05 Good reliability Each module is independent to each other, and doesn’t affect with each other.

Ozone Robot- the supplier of modular plate type ozone generator system-intellectual proptery SN application/registration number Application date The name of invention Patent types 1 201520300591. 4 2015. 05. 12 High efficiency modular plate type ozone generation and discharge unit utility model 2 201520616062. 5 2015. 08. 17 New modular plate plasma ozone generator utility model 3 201510501907. 0 2015. 08. 17 New modular plate plasma ozone generator invention 4 201520616064. 4 2015. 08. 17 Catalytic ozone destroyer utility model 5 201520616063. X 2015. 08. 17 High voltage electrode box special for ozone generator utility model 6 2015 SR 075943 2014. 09. 01 Frequency conversion control software for ozone generator Software copyright

05 Renovation scheme of flue gas denitrification

Scheme comparison item quantities SCR SNCR Renovate flue gas pipe, Renovate the bolier’s internal pipe, and add SCR reactor add pipe system of spraying ammonia Ozone oxidation Renovate partial flue gas pipe or urea Effect to boiler period Assessment of operation risk Denitrification rate No effect to boiler If there is problem, the boiler needs No effect to boiler to be shut down for maintenance longer Easy installation, period is shorter Secondary pollution and safety The reacted gas is oxygen, no safety problems such as block of urea secondary pollution, the added catalyst poisoning and spraying gun, pipe burst, ammonia pipe can’t be corroded by ammonia leakage occur leakage and slip and others problems ozone for long term operation. easily during operation. occur easily during operation. 80～ 90% 40～ 60% 80～ 95%

Scheme comparison Item SCR The ammonia fluid and urea Operation cost SNCR The ammonia fluid and Ozone oxidation Simple operation, high will be consumed continuously urea will be consumed automation, small system in operation. Catalyst continuously in management and poisoning will incur easily in operation. The maintenance personnel, only actual operation, the operation cost is consuming electricity in cost is high, the operation mainly reagents operation, no other reagents system is complicated that consumption and needed, low operating costs. need more management and maintenance personnel. Investment at once High investment(including Comparing with SCR Minimum investment at basic construction quantities, (the construction once(simple system, catalysts ) quantities is relatively construction quantities is small) small. )

The scheme confirmation of ozone oxidation 1 High safety，no poisonous gas such as ammonia liquid needed 2 Rapid reaction, high denitrification rate, almost no effect to the old boiler combustion rate. 3 No complicated control and inspect unit needed 4 Only consume electricity. Low operation cost 5 Absorption tower uses the old desulfurization tower, no new reactor needed.

06 The cases introduction of Ozone Robot ozone generator

The cases introduction of Ozone Robot ozone generator

The cases introduction of Ozone Robot ozone generator The project of desulfurization and denitrification for steel mill—— 2× 35 kg/h The project is that the ozone used for flue gas treatment of steel mill, which is the waste gas produced during steelmaking. The mill’s flue gas is 700, 000 m³/h，NOx concentration is 140 mg/m³，the 70 kg container type ozone generator of our company is selected for this item. How to select the ozone generator and calculate ： the NOx amount for removal flue gas amount×（NOX of inlet－NOX of outlet）× 10 -6 calculation of ozone dosage 1. 8 x（ NOx removal amount）＝ O 3 dosage For example： this project is 700, 000 m³/h，it requests to decrease the NOx from 140 mg/Nm 3 to 40 mg/Nm 3，the decline range is 100 calculated as: 700000×（140 -40)× 10 -6=70 kg

The cases introduction of Ozone Robot ozone generator

The cases introduction of Ozone Robot ozone generator

The cases introduction of Ozone Robot ozone generator The project of desulfurization and denitrification of waste gas for the boiler mill—— 2*9 kg/h The flue gas amount is 20000 m³， NOx concentration before dosing ozone to flue gas is 243 mg/m³， The NOx detection amount is almost null after ozone reaction into desulfurization tower and removal, The on-line data installed on spot is stabilized below 50 mg/m³. This project is that the ozone is applied for boiler flue gas treatment.

The cases introduction of Ozone Robot ozone generator The project of desulfurization and denitrification of waste gas for boiler mill—— 2*9 kg/h boiler cottrell process room ozone dosage Flue gas emission entering into secondary dust collecting tower after desulfurization tower

THANKS Ozone Robot Environmental Equipment Ltd