INTEGRATED PURIFICATION METHOD AND SYSTEM FOR THE INDUSTRIAL EXHAUST GAS CONTAINING CYANIDES, HYDROCARBONS AND NOx

Abstract

An integrated purification method and an integrated purification system for an industrial exhaust gas containing cyanides, hydrocarbons and NO.sub.x. The method comprises the steps of: 1) subjecting the exhaust gas containing pollutants such as cyanides, hydrocarbons and nitrogen oxides (NO.sub.x) to a gas-liquid separation device (1) to separate the free fluid, then mixing with the air blown by the air blower (201, 202), and preheating by the heating unit; 2) the mixture entering into the selective catalytic combustion (SCC) reactor (5) for the selective catalytic combustion reaction to convert harmful substances into CO.sub.2, H.sub.2O and N.sub.2, the catalysis being performed in two stages: the earlier stage is catalyzed by supported molecular sieve catalyst, and the latter stage is catalyzed by supported precious metal catalyst; and 3) the gas came out from the SCC reactor (5) entering into the heating unit to recover the heat, and then the purified exhaust gas being discharged directly through the chimney (6). The system comprises a gas-liquid separation device (1), a heating unit and a selective catalytic combustion reactor (5), a gas outlet of the gas-liquid separation device (1) being connected to the selective catalytic combustion reactor (5) through the heating unit, and an exhaust gas outlet of the selective catalytic combustion reactor (5) being connected to a chimney (6) through the heating unit.

Claims

1. An integrated purification method for an industrial exhaust gas of cyanides, hydrocarbons and NO.sub.x, wherein the industrial exhaust gas is an industrial exhaust gas containing multi-component pollutants, comprising: 1) subjecting the exhaust gas containing pollutants such as cyanides, hydrocarbons and nitrogen oxides to a gas-liquid separation device to separate the free fluid, then mixing with the air blown by the air blower, and preheating by the heating unit; 2) entering into the selective catalytic combustion reactor for the selective catalytic combustion reaction, wherein the catalysis is performed in two stages in the selective catalytic combustion reactor, the earlier stage is catalyzed by supported molecular sieve catalyst, and the latter stage is catalyzed by supported precious metal catalyst, the temperature of the inlet for entering into the selective catalytic combustion reactor is 280-350 C., the temperature of the catalyst in the earlier stage is controlled at 300-550 C., the temperature of the catalyst in the latter stage is controlled at 500-650 C., and the harmful substances are converted into CO.sub.2, H.sub.2O and N.sub.2 under the condition of a bed pressure of 0.5-25 kPa; and 3) the gas came out from the selective catalytic combustion reactor entering into the heating unit to recover the heat, and then the purified exhaust gas being discharged directly through the chimney.

2. The integrated purification method for the industrial exhaust gas according to claim 1, wherein in operation 1) the total oxygen volume concentration in the exhaust gas before entering into the SCC reactor is controlled by the flow rate of the air supplemented by the air blower at 3% to 8%, preferably 5%.

3. The integrated purification method for the industrial exhaust gas according to claim 1, wherein in operation 2) the temperature of the inlet of the selective catalytic combustion reactor is preferably 325 C., the temperature of the catalyst in the earlier stage bed is controlled at 43020 C., and the temperature of the catalyst in the latter stage bed is controlled at 56020 C.

4. The integrated purification method for the industrial exhaust gas according to claim 1, wherein in operation 2) the supported molecular sieve catalyst in the earlier stage is a honeycomb monolithic catalyst or granular bundling catalyst, wherein the molecular sieve is one or more molecular sieves of ZSM-5 to ZSM-48 series, Beta, Y, MCM-22 to MCM 56 series, SAPO-5 to SAPO-47 series, SBA-15, SBA16 and TS-1, the supported metal ion is one or more ions of copper, iron, cobalt, manganese, nickel, aluminum, silver and the like, preferably the honeycomb monolithic catalyst Cu-ZSM-5.

5. The integrated purification method for the industrial exhaust gas according to claim 1, wherein in operation 2) a cordierite ceramic or a metal corrugated plate is used as the matrix in the precious metal catalyst in the latter stage, the precious metal is one or more of platinum, palladium, rhodium, silver and ruthenium, and the precious metal catalyst is preferably a platinum/palladium-cordierite honeycomb ceramic catalyst.

6. The integrated purification method for the industrial exhaust gas according to claim 1, wherein in operation 2) the ratio of the catalysts filling amounts in the earlier stage and the latter stage is in the range of 1-5:0-3, preferably 3:1.

7. An integrated purification treatment system for an industrial exhaust gas containing cyanides, hydrocarbons and NO.sub.x, comprising: a gas-liquid separation device, a heating unit and a selective catalytic combustion reactor, the gas-liquid separation device is provided with a gas outlet, a pipe connecting the gas outlet is connected to an exhaust gas inlet of the selective catalytic combustion reactor through the heating unit, the pipe connecting the gas outlet is provided with an air blower; an exhaust gas outlet of the selective catalytic combustion reactor is connected to a heating medium inlet of the heating unit through a pipe, and a heating medium outlet of the heating unit is connected with a chimney.

8. The integrated purification treatment system for the industrial exhaust gas according to claim 7, wherein the heating unit includes a heat recovery device and an electric heater, wherein the heat recovery device includes a steam exchanger, an exhaust heat boiler, and an exhaust gas heat exchanger.

9. The integrated purification treatment system for the industrial exhaust gas according to claim 7, wherein the selective catalytic combustion reactor, a gas distributor, a molecular sieve honeycomb catalyst, an air re-distributor and a precious metal catalyst bed are sequentially provided in the direction from the exhaust gas inlet to the exhaust gas outlet.

10. The integrated purification treatment system for the industrial exhaust gas according to claim 7, wherein the purification treatment system for the exhaust gas includes two air blowers, wherein the outlet of the first air blower is connected to the pipe connecting the gas outlet, the outlet of the second air blower is connected to the selective catalytic combustion reactor, and the inlet position is located between the molecular sieve honeycomb catalyst and the air re-distributor.

Description

DESCRIPTION OF THE DRAWINGS

[0030] FIG. 1 is a process flow diagram of the integrated purification treatment process of the present invention.

[0031] FIG. 2 is a schematic diagram of the internal structure of SCC reactor (5) of the present invention.

[0032] In the figures, 1 is the gas-liquid separation tank, 101 is the exhaust water pipe of the gas-liquid separation tank, 201 is the first air blower, 202 is the second air blower, 301 is the electric heater, 302 is the steam exchanger, 303 is the exhaust gas heat exchanger, 4 is the exhaust heat boiler, 401 is the water supply pipe of the boiler, 402 is the water vapor emptying device, 403 is the sewage pipe of the boiler, 5 is the SCC reactor, 501 is the exhaust gas inlet, 502 is the gas distributor, 503 is the molecular sieve honeycomb catalyst bed, 504 is the air re-distributor, 505 is the precious metal catalyst bed, 506 is the exhaust gas outlet, 6 is the chimney, and 7 is the air filter.

BEST MODE OF THE INVENTION

[0033] The present invention will be described through the following preferable examples. It will be understood by a person skilled in the art that the examples are only illustrative of the invention and are not intended to limit the scope of the present invention.

[0034] In the examples, unless otherwise specified, the used means are conventional means in the art.

[0035] The catalyst used in the examples is the catalyst developed by Beijing University of Chemical Technology. The main parameters of the catalyst are shown in Table 1.

TABLE-US-00001 TABLE 1 Main Parameters of the Catalyst Molecular Precious metal sieve honeycomb catalyst ceramic catalyst Type of the catalyst Honeycomb Honeycomb The main active ingredients Cu Pt and Pd The weight percentage content of the 3~6 Pt 0.13, main active ingredients (wt %) Pd 0.05 The components of the supporter ZSM-5 Cordierite Pore density CPSI 110 110 Pitch-row mm 2.4 2.4 Open area % 60 60 Catalyst density kg/m.sup.3 670 490 The sectional dimension of mm 75 150 the catalyst block-length The sectional dimension of mm 75 150 the catalyst block-wide The catalyst block-high mm 75 150
In Table 1, the catalyst block is the outer dimension of the honeycomb catalyst.

EXAMPLE 1

[0036] The conditions of Examples 1 and 2 and Comparative Examples 1 and 2 were the simulation of the system constituted by the main gas in the exhaust gas of Example 3, and they are the experiments conducted in the laboratory with gas cylinders.

[0037] The experimental results of selective catalytic reduction of NO.sub.x by the molecular sieve catalysts at different oxygen concentrations were individually investigated in this Example, wherein propylene and propane were used as the reducing agents. The experimental conditions were: NO(200 mg/m.sup.3)+C.sub.3H.sub.6(2000 mg/m.sup.3)+C.sub.3H.sub.8(2000 mg/m.sup.3)+CO(5000 mg/m.sup.3), and the oxygen concentration was 5% (volume percentage, similarly hereinafter).

[0038] The molecular sieve honeycomb catalyst (Cu-ZSM-5) was used in the earlier stage, the honeycomb ceramic catalyst containing precious metal (the main components were platinum and palladium) was used in the latter stage, and the ratio of the filling amounts of the catalysts in the earlier stage and the latter stage was 3:1.

EXAMPLE 2

[0039] The experimental conditions of Example 2 were: NO(200 mg/m.sup.3)+C.sub.3H.sub.6(2000 mg/m.sup.3)+C.sub.3H.sub.8(2000 mg/m.sup.3)+CO(5000 mg/m.sup.3), and the oxygen concentration was 8%.

COMPARATIVE EXAMPLE 1 AND COMPARATIVE EXAMPLE 2

[0040] In Comparative Examples 1 and 2, the oxygen concentrations were 10% and 12%, respectively. Other experimental conditions were the same as that in Example 1, and the obtained results were shown in Table 2.

TABLE-US-00002 TABLE 2 Effects of different oxygen concentrations on the removal of NO.sub.x by molecular sieve catalysts Comparative Comparative Example 1 Example 2 Example 1 Example 2 Temperature ( C.) NO mg/m.sup.3 NO mg/m.sup.3 NO mg/m.sup.3 NO mg/m.sup.3 350 130 152 167 170 400 105 110 152 164 450 81 91 114 142 500 96 98 110 154 550 116 120 139 176

[0041] It can be seen from Examples 1 and 2 and Comparative Examples 1 and 2 that, in the molecular sieve catalyst bed, when the oxygen concentration is higher than 8%, the removal effect of NO.sub.x is poor. Meanwhile, when the temperature is higher than 500 C., the removal of NO.sub.x by the molecular sieve catalyst cannot reach the discharge standard. The higher oxygen concentration and higher temperature are not conducive to the removal of NO.sub.x, it may be that propylene or propane cannot play the role of a reducing agent, and all of them were carried out the oxidation reaction. Therefore, the oxygen concentration of the exhaust gas must be controlled no higher than 8%, and the temperature of the molecular sieve catalyst bed cannot be higher than 550 C.

[0042] Therefore, the integrated purification treatment for the industrial exhaust gas containing multi-component pollutants such as cyanides, hydrocarbons and NO.sub.x, can be achieved by the manner of combination catalysis and the reasonable design through precisely controlling the reaction conditions.

EXAMPLE 3

[0043] Referring to FIG. 1, which showed an integrated purification treatment process for the exhaust gas produced by acrylonitrile production device, the used system includes a gas-liquid separation tank 1, a heating unit, and a SCC reactor 5.

[0044] The gas-liquid separation tank 1 was provided with a gas outlet, a pipe connecting the gas outlet was connected to an exhaust gas inlet of the SCC reactor through the heating unit, the pipe connecting the gas outlet was provided with an air blower; an exhaust gas outlet of the SCC reactor was connected to the heating medium inlet of the heating unit through a pipe, and a heating medium outlet of the heating unit was connected with a chimney.

[0045] Wherein, the heating unit included a heat recovery device and an electric heater 301, and the heat recovery device included a steam exchanger 302, an exhaust heat boiler 4, and an exhaust gas heat exchanger 303. The accessories of the exhaust heat boiler 4 included a water supply pipe of the boiler 401 connecting the pipe network, a sewage pipe of the boiler 403 discharged to the sewage system, and a water vapor emptying device 402.

[0046] Referring to FIG. 2, in the SCC reactor 5, a gas distributor 502, a molecular sieve honeycomb catalyst bed 503, an air re-distributor 504, and a precious metal catalyst bed 505 were sequentially provided in the direction from the exhaust gas inlet 501 to the exhaust gas outlet 506.

[0047] The purification treatment system for the exhaust gas of the present Example included two air blowers, the air inlets thereof were connected to an air filter 7, the air inflow included air and nitrogen from the pipe network; wherein the outlet of the first air blower 201 was connected to the pipe connecting the gas outlet, the outlet of the second air blower was connected to the SCC reactor, and the inlet position was located between the molecular sieve honeycomb catalyst bed 503 and the air re-distributor 504.

[0048] The exhaust gas from the absorption tower of the acrylonitrile production separation device was subject to a gas-liquid separation tank 1 to separate the free fluid, and then mixed with air, and the air replenishment amount should be adjusted according to the controlled total oxygen concentration in exhaust gas (3% to 8%); after the pre-heating by the exhaust gas heat exchanger 303, wherein the electric heater in the process flow was used only at the driving mode, and was normally in the closed state, the pre heated exhaust gas enters the SCC reactor 5 for selective catalytic combustion reaction; in the fixed bed reactor, the catalyst bed was divided into two stages by the air re-distributor, the earlier stage was catalyzed by the supported molecular sieve honeycomb catalyst, and the later stage was catalyzed by the supported precious metal catalyst; the temperature of the inlet of the reactor was 280-350 C., the temperature of the catalyst in the earlier stage was 300-550 C., the temperature of the catalyst in the latter stage was 500-650 C. and the harmful substances were converted into CO.sub.2, H.sub.2O and N.sub.2 under the conditions of a bed pressure of 0.5-25 kPa(G) (a pressure drop which can be tolerated by the catalyst bed in the reactor). Wherein, the later bed temperature control was performed by appropriate replenishment by using blower according to the condition of the temperature rise of the reaction heat release. The purified gas from the SCC reactor was subject to the heat recovery devices such as steam superheater, exhaust heat boiler, and exhaust gas heat exchanger to recover heat, and then discharged directly through the chimney.

[0049] The specific processes and effects are reflected in the following tests.

EXAMPLE 4

[0050] 1) The exhaust gas containing pollutants such as cyanides, hydrocarbons and nitrogen oxides was firstly subjected to a gas-liquid separation device to separate the free fluid, then mixed with the air blown by the first air blower 201, and preheated by the heating unit;

[0051] 2) after entering into the SCC reactor 5 for the selective catalytic combustion reaction, the catalysis was performed in two stages in the SCC fixed bed reactor R-101, the catalyst bed was divided into two stages by the air re-distributor 504 in the reactor, the earlier stage was catalyzed by the supported molecular sieve catalyst, and the latter stage was catalyzed by the supported precious metal catalyst, the temperature of the inlet for entering into the SCC reactor was 280 C., the temperature of the catalyst in the earlier stage was controlled at 338 C., the temperature of the catalyst in the latter stage was controlled at 518 C., and the harmful substances were converted into CO.sub.2, H.sub.2O and N.sub.2 under the condition of a bed pressure of 0.5-25 kPa(G); and

[0052] 3) the gas came out from the SCC reactor 5 was subject to the heat recovery devices such as steam superheater 301, exhaust heat boiler 4, and exhaust gas heat exchanger 303 to recover heat, and the purified exhaust gas was discharged directly through the chimney 6.

[0053] The exhaust gases of Examples 4-9 and Comparative Examples 3-8 were derived from a company's 106,000 ton/year of acrylonitrile production device, the exhaust gas purification treatment system was the same as that of Example 3, and the working conditions were shown in Table 3:

TABLE-US-00003 TABLE 3 The components of the exhaust gas from a company's absorption tower Monitoring items Numerical value The total flow of the exhaust gas (m.sup.3/h) 50000~70000 Acrylonitrile (mg/Nm.sup.3) 100~620 Total non-methane hydrocarbon (mg/m.sup.3) 7000~12500 Propane (mg/m.sup.3) 1000~3012 Propylene (mg/m.sup.3) 1201~3059 Ethane (mg/m.sup.3) 10~400 Hydrocyanic acid (mg/Nm.sup.3) 0~60 Acetonitrile (mg/Nm.sup.3) 0~50 Nitrogen oxides(mg/m.sup.3) 200~435 Oxygen concentration (%) 1.1~7.2 Nitrogen (%) 89~91 Temperature ( C.) 35 The pressure of the exhaust gas inlet kPa (G) 20

EXAMPLES 5-9

[0054] In Example 4 to Example 9, a molecular sieve honeycomb catalyst (the main component was Cu-ZSM-5) was used in the earlier stage of the SCC reactor, a precious metal honeycomb ceramic catalyst (platinum/palladium-cordierite honeycomb ceramic catalyst) was used in the later stage, and the ratio of the catalysts filling amounts in the earlier stage and the latter stage was 3:1, the pressure in the reactor was about 5 kPa (G), and the removal effect of the exhaust gas was controlled by adjusting the temperatures of the inlet and the catalyst bed. The other process conditions were the same as those in Example 4, and the results were shown in Table 4.

TABLE-US-00004 TABLE 4 Test data obtained from Examples 4-9 and the national emission standard National emission standard Items Unit and name Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 mg/m.sup.3 Temperature Inlet ( C.) 280 325 347 327 338 327 The 338 432 451 488 469 454 temperature of 460 489 504 533 516 525 the molecular sieve catalyst bed ( C.) The 518 547 553 648 570 608 temperature of the precious metal catalyst bed ( C.) Outlet ( C.) 512 568 560 644 574 611 Outlet Total 119 110 100 78 105 84 120 concentration non-methane (mg/m.sup.3) hydrocarbon NO.sub.x 77 89 94 99 84 93 100 Acrylonitrile 2.6 5.2 5.6 3.6 5 4.5 22 Hydrocyanic 1 1.2 0.5 0 0 0 1.9 acid Acetonitrile 3 1 4.9 0 1.1 0 none

COMPARATIVE EXAMPLES 3-5

[0055] In Comparative Example 3 to Comparative Example 5, the molecular sieve honeycomb catalyst (the main component was Cu-ZSM-5) was used in the earlier and later stages of the SCC reactor, and the other process conditions were the same as those in Example 4, and the results were shown in Table 5.

TABLE-US-00005 TABLE 5 Test data obtained from the Comparative Example in which the molecular sieve catalyst was the only catalyst used and the national emission standard National Comparative Comparative Comparative emission Example Example Example standard Items Unit and name 3 4 5 mg/m.sup.3 Temperature Inlet ( C.) 295 325 345 The bed temperature in 307 432 559 the reactor in which the 378 489 609 molecular sieve catalyst 440 537 625 was only used ( C.) Outlet ( C.) 519 539 625 Outlet Total non-methane 1210 756 109 120 concentration hydrocarbon (mg/m.sup.3) NO.sub.x 82 98 121 100 Acrylonitrile 6.5 3.0 0.5 22 Hydrocyanic acid 0.6 1.1 0 1.9 Acetonitrile 1.1 2.4 0 none

[0056] In Comparative Examples 3 and 5, when the molecular sieve catalyst was the only catalyst used in the SCC reactor, the NO.sub.x can reach the national emission standard at low temperature, however, the NO.sub.x cannot reach the discharge standard when the temperature is higher than 600 C. With regard to hydrocarbons, it cannot reach the discharge standard at low temperature, while it can reach the discharge standard at high temperature. But the high temperature is not conducive to the removal of NO.sub.x, and the catalyst cannot tolerate the high temperature of 600 C. or more for a long time.

COMPARATIVE EXAMPLES 6-8

[0057] In Comparative Example 6 to Comparative Example 8, the honeycomb ceramic catalyst containing precious metal (the main components were platinum and palladium) was used in the earlier and latter stages of the SCC reactor, and the results were shown in Table 6.

TABLE-US-00006 TABLE 6 Test data obtained from the Comparative Examples in which the precious metal catalyst was the only catalyst used and the national emission standard National emission Comparative Comparative Comparative standard Items Unit and name Example 6 Example 7 Example 8 mg/m.sup.3 Temperature Inlet ( C.) 344 280 305 The bed temperature 575 520 539 in the reactor in 576 521 541 which the precious metal catalyst was 571 525 545 only used ( C.) Outlet ( C.) 576 524 561 Outlet Total non-methane 81 102 99 120 concentration hydrocarbon (mg/m.sup.3) NO.sub.x 982 798 921 100 Acrylonitrile 6.5 12.0 9.4 22 Hydrocyanic add 0.6 1.1 0 1.9 Acetonitrile 1.1 2.4 0 none

[0058] It can be seen from Examples 4 to 9 that, the substances containing cyanide, hydrocarbons and NO.sub.x can be removed and reach the national emission standard by the manner of combing the molecular sieve catalyst in the earlier stage and the precious metal catalyst in the latter stage and controlling the temperature in the SCC reactor.

[0059] The above results show that the integrated purification treatment for the industrial exhaust gas containing multi-component pollutants such as cyanides, hydrocarbons and NO.sub.x can be achieved by the manner of combination catalysis and reasonable design through precisely controlling the reaction conditions.

[0060] The embodiments described above are merely preferred embodiments of the present invention, but not intended to limit the scope of the invention. Those skilled in the art may make various modifications and improvements to the technical solutions of the present invention without departing from the designing spirit, which all fall within the protection scope defined by the appended claims of the invention.

INDUSTRIAL APPLICABILITY

[0061] The present invention provides an integrated purification method for the industrial exhaust gas of cyanides, hydrocarbons and NO.sub.x, wherein the exhaust gas is an industrial exhaust gas containing multi-component pollutants. The method comprises the steps of: subjecting the exhaust gas containing pollutants such as cyanides, hydrocarbons and nitrogen oxides (NO.sub.x) to a gas-liquid separation device to separate the free fluid, then mixing with the air blown by the air blower, and preheating by the heating unit; then entering into the SCC reactor for the selective catalytic combustion reaction, the gas came out from the SCC reactor entering into the heating unit to recover the heat, and then the purified exhaust gas being discharged directly through the chimney. The present invention can achieve the conversion of three pollutants containing cyanides (RCN), hydrocarbons (C.sub.xH.sub.y) and nitrogen oxides (NO.sub.x) simultaneously in the same reactor by reasonably installing the catalysts with different functions, without installing individual selective catalytic reduction denitration reactor and additional ammonia, and significantly simplifies the process. The present invention can achieve the exhaust gas treatment in multi-industry and multi-working conditions by adjusting the combination mode of the catalysts, and has wide application prospect.