CN107433127B - Method and device for catalytic oxidation purification and energy utilization of low-calorific-value industrial tail gas - Google Patents
Method and device for catalytic oxidation purification and energy utilization of low-calorific-value industrial tail gas Download PDFInfo
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- CN107433127B CN107433127B CN201710645200.6A CN201710645200A CN107433127B CN 107433127 B CN107433127 B CN 107433127B CN 201710645200 A CN201710645200 A CN 201710645200A CN 107433127 B CN107433127 B CN 107433127B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/869—Multiple step processes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G5/00—Incineration of waste; Incinerator constructions; Details, accessories or control therefor
- F23G5/44—Details; Accessories
- F23G5/46—Recuperation of heat
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
- F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
Abstract
A method and a device for complete catalytic oxidation purification and heat utilization of low-heat value industrial tail gas are composed of an air compressor, a heat exchanger, a starting heater, a catalytic reactor with a multi-stage structure, a catalyst, a dust removal purifier, a waste heat boiler, heat utilization equipment, a static mixer and a detection control component. Mixing low-heat value and low-concentration industrial tail gas with compressed air, then feeding the mixture into a catalytic reactor with a multi-stage structure, carrying out multiple catalytic oxidation reactions under the catalytic action of a catalyst to obtain purified gas, and respectively carrying out different heat recovery and capacity recovery according to the difference of heat generated by the oxidation reactions and the self pressure of the tail gas. The industrial tail gas with low heat value and low concentration is completely catalyzed, oxidized and purified and then discharged into the atmosphere. The technical scheme effectively solves the problems of purification and heat utilization of low-heat-value and low-concentration industrial tail gas, not only solves the problem of environmental-friendly emission up to the standard of the industrial tail gas, but also achieves the high-efficiency utilization of low-grade resources, and finally realizes environmental protection and economic double harvest.
Description
Technical Field
The invention belongs to the field of environmental protection and low-grade resource utilization. The industrial tail gas with low heat value (containing combustible components but low concentration, generally the combustible component content is less than 15%) is completely catalyzed, oxidized and purified and then discharged after reaching the standard, and meanwhile, the energy of the industrial tail gas is fully recycled, so that the aims of emission reduction and energy conservation are fulfilled.
Background
The industrial tail gas with high calorific value and high concentration can be recycled by being returned to a system after being pressurized, or can be used as other chemical raw materials or directly used as fuel.
But has little significance for pressurizing and recycling industrial tail gas with low heat value and low concentration or using the industrial tail gas as a raw material. And because the calorific value is lower, the fuel can not be directly ignited or can be directly ignited, but stable combustion can not be realized, and the fuel has more problems when being used as fuel. How to realize environmental protection and economic utilization is a problem of continuous research in the industry.
In low heat value and low concentration industrial tail gas, the general combustible components of CO and H2HC (alkane, alkyne, alkene, benzene, ether, phenol, ester, alcohol and derivatives thereof and the like) has a gross calorific value of less than 2500kJ/Nm3. Due to its low effective component content and other inert gases (such as N)2、CO2Etc.) is relatively high, if recycled, the treatment cost is too high, and the economical efficiency is poor; if the fuel gas is used as fuel gas, stable and reliable combustion is difficult to realize. In the prior art, industrial enterprises basically adopt a direct emptying mode or an emptying mode after combustion to process the industrial tail gas. The industrial tail gas cannot reach the standard and is discharged, so that the environment is polluted, and meanwhile, energy (heat energy and pressure potential energy) is wasted. With the development of catalyst technology, catalytic purification processes are beginning to be used for the treatment of industrial exhaust gases. For example, the "carbon catalytic reduction treatment method of nitrous oxide in industrial tail gas" disclosed in CN102974216A and the "continuous dearsenification and carbonization agent for industrial tail gas purification and preparation method thereof" disclosed in CN104624223A still fail to solve the problems of catalytic purification and energy utilization of low-heat value and low-concentration industrial tail gas. In addition, a catalytic purification method is utilizedThe granular catalyst in the prior art is not wear-resistant, has short service life (only about 3 years), high resistance and low airspeed (5000 h) when used for treating low-heat-value and low-concentration industrial tail gas-1In the anoxic condition state of the catalyst), the carbon deposition problem causes the service life of the catalyst to be shortened, and the catalyst regeneration process for treating the carbon deposition problem causes the catalytic combustion process to become complicated, the investment is increased, the adaptability of the catalyst is relatively weak, and combustible components in tail gas cannot be effectively oxidized.
Disclosure of Invention
The invention aims to provide a method and a device for catalytic oxidation purification and energy utilization of low-heat-value industrial tail gas, which are used for mixing low-heat-value and low-concentration industrial tail gas with compressed air in batches and carrying out complete catalytic oxidation in grades. In the catalytic reactor, the peroxide state is always kept, so that combustible components in the industrial tail gas are subjected to complete oxidation reaction through catalytic action, and the energy of the tail gas is fully recycled according to the difference of the heat value and the pressure of the tail gas. The method overcomes the defects in the prior art, and provides a new technical scheme for effectively solving the problems of catalytic purification and energy utilization of low-heat-value industrial tail gas.
The invention is realized by the following technical scheme:
a method for catalytic purification and heat utilization of low-calorific-value industrial tail gas is remarkably different from the prior art in that: the flow rate is 500-40000 Nm3The method comprises the steps of firstly shunting 34% of industrial tail gas with the total combustible component content of 5-15% at normal temperature under the pressure of 40-2000 KpaG, fully mixing the industrial tail gas with compressed air from an air compressor and with the excess coefficient of 1.05-1.5, heating the industrial tail gas to 180-350 ℃ by a starting heater, sending the industrial tail gas into a first stage of a catalytic reactor for catalytic oxidation reaction, heating the purified mixed gas to 400-600 ℃, sending the industrial tail gas into a waste heat boiler for recycling heat, shunting 50% of the residual industrial tail gas, fully mixing the industrial tail gas with the mixed gas subjected to heat exchange in the first stage, controlling the temperature to 180-350 ℃, sending the industrial tail gas into a second stage of the catalytic reactor for catalytic oxidation reaction, heating the purified mixed gas to 400-600 ℃, sending the industrial tail gas into the waste heat boiler for recycling heat, and finally conducting 50% ofAnd fully mixing the industrial tail gas with the mixed gas subjected to the second-stage heat exchange, controlling the temperature to be 180-350 ℃, sending the mixed gas into a third stage of a catalytic reactor for catalytic oxidation reaction, heating the purified mixed gas to 400-600 ℃, returning the purified mixed gas into a heat exchanger to heat the compressed air to 180-350 ℃, turning off a heater, and finally discharging the purified mixed gas to the atmosphere after reaching the standard through heat utilization equipment.
The device for catalytic purification and heat utilization of the low-calorific-value industrial tail gas based on the method comprises an air compressor, a heat exchanger, a starting heater, a catalytic reactor with a multi-stage structure, a catalyst, a dust removal purifier, a waste heat boiler, heat utilization equipment and a matched detection control component, and is distinguished from the prior art by the following outstanding differences: the method comprises the steps of connecting a low-heat-value low-concentration industrial tail gas pipeline to a compressed air pipeline, connecting an inlet of a heat exchanger, connecting an outlet of the heat exchanger to a starting heater and then to a first-stage input port of a catalytic reactor, connecting a first-stage output port of the catalytic reactor to an inlet of a waste heat boiler, connecting an outlet of the waste heat boiler to a low-heat-value low-concentration industrial tail gas pipeline, connecting a second-stage input port of the catalytic reactor, connecting a second-stage output port of the catalytic reactor to the inlet of the waste heat boiler, connecting an outlet of the waste heat boiler to a third-stage input port of the catalytic reactor after connecting the outlet of the waste heat boiler to the low-heat-value low-concentration industrial tail gas pipeline, repeating the steps until a last-stage output port of the catalytic reactor is connected to. The outlet of the heat utilizing device is connected to the atmosphere.
The method and the device for treating the low-calorific-value industrial tail gas have the following advantages:
1) the process of adding tail gas into air in a grading manner is adopted, so that the content of combustible gas is ensured to be within a safe concentration range below an explosion lower line, the running safety of the device is ensured, the temperature of each bed layer catalyst of a catalytic reactor is ensured to be below a safe temperature line, the whole catalytic reaction is always in a peroxide state, and the problem of carbon deposition of the catalyst is effectively reduced or solved;
2) the catalyst adopts a honeycomb type integral structure, and the space velocity is high (1)0000-40000h-1) Low resistance, strong anti-breakage and abrasion ability and long service life;
3) according to the difference of combustible components of the tail gas, the corresponding formula of the active components of the catalyst is adjusted, the co-catalytic oxidation of the catalyst on multiple components in the tail gas is enhanced, and the environmental protection performance and the energy recovery rate of the device are greatly improved;
4) according to the difference of the pressure of tail gas, flexible and various energy recycling modes can be adopted according to the actual conditions of a factory, the pressure after the tail gas is discharged from a final stage reactor is 0.6MPaG, heat and pressure energy are recycled in a power generation mode, the pressure is lower than 0.6MPaG, heat is recycled by using waste heat boiler byproduct steam, or partial heat and pressure potential energy (rich heat and pressure potential energy are fully utilized) are recycled and then are used for drying or heating materials;
5) the reaction can be carried out in one stage or multiple stages according to the amount of tail gas and the heat value, and the preparation is flexible, economic and applicable;
6) the heat of the first-stage reaction and the second-stage reaction is used for producing steam, and the heat of the third-stage reaction is used for heating the gas at the inlet of the first stage, so that the regulation and control of the temperature at the inlet of the second-stage reaction and the temperature at the inlet of the third-stage reaction are facilitated, the operation is flexible, and the safety and stability are higher.
The invention effectively solves the problems of high treatment cost, poor economy, unstable combustion and difficult use in industrial equipment, and overproof discharge caused by direct emptying or emptying after combustion accompanying, which not only pollutes the environment, but also wastes the low calorific value of energy in the prior art of low-calorific value industrial tail gas, and realizes the dual effects of environmental-friendly standard discharge of industrial tail gas and high-efficiency utilization of low-calorific value and low-concentration resources.
The invention is elucidated below with reference to the drawings and embodiments.
Drawings
Fig. 1 is a schematic diagram of the principle and structure of the present invention.
The specific implementation mode is as follows:
the following examples are intended to further describe and explain the present invention in detail, but are not intended to limit the invention in any manner. Any simple modifications and substitutions of the present invention by a person of ordinary skill in the art are within the scope of the present invention.
Example 1:
the flow rate is 500Nm3H, 41kpa G pressure, 35 ℃ temperature, 5% combustible content, 300Nm from the air compressor main3And h, after air with the pressure of 40 kpa G is fully mixed, the air is heated to 350 ℃ by a starting heater, the air is sent into a catalytic reactor for complete catalytic oxidation and then heated to 489 ℃, the high-temperature mixed gas after reaction is led out from an outlet of the reactor, enters an inlet heater of the reactor to heat the inlet gas to 360 ℃, is cooled and then is discharged to the atmosphere. The indexes of all components of the mixed gas discharged from the catalytic reactor meet the national emission requirement. Because of small gas quantity, low pressure and no energy recovery value.
Example 2:
the flow rate is 24000Nm3At a pressure of 200kpa G and a temperature of 25 ℃, with a total combustible content of 11% industrial tail gas, split flow of 8000Nm315500 Nm/h from main pipe of air compressor3H, after the air with the pressure of 210kpa G is fully mixed, the air is heated to 220 ℃ by a starting heater and sent to the first stage of a catalytic reactor for complete catalytic oxidation reaction, the mixed gas is purified, meanwhile, the reaction heat heats the mixed gas to 583 ℃, the high-temperature gas after the first stage of reaction passes through a waste heat boiler, the heat is recycled, the steam is by-produced, the temperature is reduced to 370 ℃, and 8000Nm of residual tail gas is shunted3And h, fully mixing the mixed gas after heat exchange with the primary outlet, sending the mixed gas into a secondary stage of a catalytic reactor for complete catalytic oxidation reaction, and heating the mixed gas to 580 ℃ by reaction heat while purifying the mixed gas. The high-temperature gas after the second-stage reaction passes through a waste heat boiler, the heat is recycled, the steam byproduct is cooled to 330 ℃, and finally the residual whole tail gas is introduced with 8000Nm3And h, fully mixing the mixed gas after heat exchange with the second-stage outlet, sending the mixed gas into the third stage of the catalytic reactor for complete catalytic oxidation reaction, and heating the mixed gas to 580 ℃ by reaction heat while purifying the mixed gas. Introducing the high-temperature gas from the outlet of the third stage into the first-stage inlet heat exchanger for heating the gas at the inlet of the first stage to 230 ℃ (to reach the temperature of the gas at the inlet of the third stageTemperature of activation is started, heater is started after the activation is stopped), and the third-stage outlet gas is cooled and is used for reaching the standard after the drying of the materials and discharged to the atmosphere through heat utilization equipment.
Example 3:
the flow rate is 40000Nm313000Nm of industrial tail gas as a total combustible component at 23 ℃ under a pressure of 2000kpa G325500Nm from the air compressor manifold3And h, after fully mixing air with the pressure of 2000kpa G, heating the air to 235 ℃ by a starting heater, sending the air to the first stage of a catalytic reactor for complete catalytic oxidation reaction, and heating the mixed gas to 590 ℃ by reaction heat while purifying the mixed gas. The high-temperature gas after the first-stage reaction passes through a waste heat boiler, the heat is recycled, the steam is byproduct, the temperature is reduced to 310 ℃, and 13000Nm of the residual tail gas is shunted3And/h, fully mixing the mixed gas after heat exchange with the first-stage outlet, sending the mixed gas into a second stage of the catalytic reactor for complete catalytic oxidation reaction, and heating the mixed gas to 596 ℃ by reaction heat while purifying the mixed gas. The high-temperature gas after the second-stage reaction passes through a waste heat boiler, the heat is recycled, the steam byproduct is cooled to 350 ℃, and finally the residual whole tail gas 14000Nm is introduced3And h, fully mixing the mixed gas after heat exchange with the second-stage outlet, sending the mixed gas into the third stage of the catalytic reactor for complete catalytic oxidation reaction, and heating the mixed gas to 594 ℃ by reaction heat while purifying the mixed gas. High-temperature gas after the third-stage reaction is used for heating first-stage inlet gas to 240 ℃ (the temperature reaches the activation temperature and the heater is started after the first-stage inlet heat exchanger is turned off), and after the high-temperature gas is cooled to 350 ℃, the third-stage outlet gas is cooled and used for being discharged after power generation and also can be discharged to the atmosphere after being dried after reaching the standard through heat utilization equipment.
A device for catalytic purification and heat utilization of low-heat value industrial tail gas based on the method comprises an air compressor 1, a heat exchanger 2, a starting heater 3, a catalytic reactor 4 with a multi-stage structure, a catalyst 5, a dust removal purifier 6, a waste heat boiler 7, heat utilization equipment 8 and matched detection control components, wherein the low-heat value and low-concentration industrial tail gas pipeline is connected with a compressed air pipeline and then is connected to an inlet of the heat exchanger 2, an outlet of the heat exchanger 2 is connected with the starting heater 3 and then is connected with a first-stage input port of the catalytic reactor 4, a first-stage output port of the catalytic reactor 4 is connected with an inlet of the waste heat boiler 7, an outlet of the waste heat boiler 7 is connected with the low-heat value and low-concentration industrial tail gas pipeline and then is connected to a second-stage input port of the catalytic reactor 4, a second-stage output port of the catalytic reactor 4, and after an outlet of the waste heat boiler 7 is connected with a low-heat-value and low-concentration industrial tail gas pipeline, connecting to a third-stage input port of the catalytic reactor 4, repeating the steps until a final-stage output port of the catalytic reactor 4 is connected with an inlet of the heat exchanger 2, and an outlet of the heat exchanger 2 is connected with an inlet of the heat utilization equipment 8. The outlet of the heat utilization device 8 is connected to the atmosphere.
The industrial tail gas with low heat value and low concentration is added into the compressed air, so that the whole catalytic purification process is in a peroxide reaction state, and the problem of carbon deposition of the catalyst is effectively reduced or solved.
The technical contents not described in detail in the present invention are all known techniques.
Claims (2)
1. A method for catalytic purification and heat utilization of low-calorific-value industrial tail gas is characterized by comprising the following steps: the flow rate is 500-40000 Nm3H, the pressure is 40-2000K PaG, the temperature is normal temperature, the industrial tail gas with 5-15% of total combustible component content is firstly shunted by 34%, and is fully mixed with compressed air from an air compressor and with the excess coefficient of 1.05-1.5, the mixture is heated to 180-350 ℃ by a starting heater and then is sent to a catalytic reactorCarrying out catalytic oxidation reaction in the first stage, heating the purified mixed gas to 400-600 ℃, sending the heated mixed gas into a waste heat boiler, recycling heat, shunting the rest industrial tail gas by 50 percent, fully mixing the industrial tail gas with the mixed gas subjected to the first-stage heat exchange, controlling the temperature to be 180-350 ℃, sending the mixed gas into a second stage of a catalytic reactor for catalytic oxidation reaction, heating the purified mixed gas to 400-600 ℃, sending the mixed gas into a waste heat boiler for recycling heat, fully mixing 50% of the industrial tail gas with the mixed gas subjected to the second-stage heat exchange, controlling the temperature to be 180-350 ℃, sending the industrial tail gas into a third stage of the catalytic reactor for catalytic oxidation reaction, heating the purified mixed gas to 400-600 ℃, sending the purified mixed gas back into a heat exchanger for heating compressed air to 180-350 ℃, and (4) stopping the heater, starting the heater, and discharging the finally purified mixed gas to the atmosphere after reaching the standard through heat utilization equipment.
2. The method for catalytic purification and heat utilization of low heating value industrial tail gas according to claim 1, characterized in that: the device for catalytic purification and heat utilization of low-heat value industrial tail gas comprises an air compressor (1), a heat exchanger (2), a starting heater (3), a catalytic reactor (4) with a multi-stage structure, a catalyst (5), a dust removal purifier (6), a waste heat boiler (7), heat utilization equipment (8) and matched detection control components, wherein a low-heat value and low-concentration industrial tail gas pipeline is connected with a compressed air pipeline and then connected to an inlet of the heat exchanger (2), an outlet of the heat exchanger (2) is connected with the starting heater (3) and then connected with a first-stage input port of the catalytic reactor (4), a first-stage output port of the catalytic reactor (4) is connected with an inlet of the waste heat boiler (7), an outlet of the waste heat boiler (7) is connected with the low-heat value and low-concentration industrial tail gas pipeline and then connected to a second-stage input port of the catalytic reactor (4, and a second-stage output port of the catalytic reactor (4) is connected with an inlet of a waste heat boiler (7), an outlet of the waste heat boiler (7) is connected with a low-heat-value and low-concentration industrial tail gas pipeline and then connected with a third-stage input port of the catalytic reactor (4), the steps are repeated until a last-stage output port of the catalytic reactor (4) is connected with an inlet of the heat exchanger (2), an outlet of the heat exchanger (2) is connected with an inlet of the heat utilization equipment (8), and an outlet of the heat utilization equipment (8) is connected with the atmosphere.
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| CN110207139A (en) * | 2019-06-18 | 2019-09-06 | 浙江宏电环保设备制造有限公司 | RTO waste gas treatment equipment |
| CN110732239A (en) * | 2019-09-17 | 2020-01-31 | 天津市华邦科技发展有限公司 | Catalytic oxidation process for high-concentration organic gas tail gas |
| CN111780140B (en) * | 2020-07-30 | 2020-12-22 | 南京大学环境规划设计研究院股份公司 | Heat accumulating type catalytic combustion device for VOCs treatment |
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| CN105650651B (en) * | 2014-12-05 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of purifying treatment method of high-concentration organic waste gas |
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| CN101301580A (en) * | 2008-06-20 | 2008-11-12 | 上海东化环境工程有限公司 | Tail gas treatment process of butane method maleic anhydride device |
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Effective date of registration: 20230625 Address after: No. 988, Keji Road, high tech Industrial Development Zone, Kunming, Yunnan 650000 Patentee after: Yunnan Precious Metals Laboratory Co.,Ltd. Address before: 650106 No. 988 Science and Technology Road, Kunming High-tech Development Zone, Yunnan Province Patentee before: SINO-PRECIOUS METALS HOLDING CO.,LTD. |