CN106861393B - Fermentation tail gas purification treatment method - Google Patents
Fermentation tail gas purification treatment method Download PDFInfo
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- CN106861393B CN106861393B CN201710120254.0A CN201710120254A CN106861393B CN 106861393 B CN106861393 B CN 106861393B CN 201710120254 A CN201710120254 A CN 201710120254A CN 106861393 B CN106861393 B CN 106861393B
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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
- B01D53/75—Multi-step processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D50/00—Combinations of methods or devices for separating particles from gases or vapours
- B01D50/20—Combinations of devices covered by groups B01D45/00 and B01D46/00
Abstract
The invention discloses a fermentation tail gas purification treatment method, which belongs to the field of industrial tail gas comprehensive treatment, and comprises the treatment steps of pretreatment, molecular sieve treatment, catalytic oxidation, alkali washing, secondary oxidation and water washing. The invention greatly reduces the use of spray towers and absorption liquid, reduces the tail gas treatment cost, has high treatment efficiency and good purification effect, and can ensure that the fermentation tail gas is safely discharged up to the standard.
Description
Technical Field
The invention relates to a gas purification treatment method, in particular to a fermentation tail gas purification treatment method, and belongs to the field of industrial tail gas comprehensive treatment.
Background
The main components of the fermentation tail gas are air and water vapor, but trace volatile organic compounds, odor gas generated in the fermentation, non-methane total hydrocarbon and other harmful substances can be carried, and the environment can be polluted to a certain extent when the harmful substances are directly discharged into the atmosphere. With the increasing awareness of environmental protection, emission standards and regulatory force on industrial tail gas are more strict, and fermentation tail gas is forbidden and penalized by relevant regulatory departments when being directly emitted without being treated.
The common fermentation tail gas purification treatment method comprises the steps of oxidizing through an oxidation tower, absorbing through an alkaline washing tower, and finally absorbing through a water washing tower and then discharging. Because the kinds of harmful substances in the fermentation tail gas are various and the concentration is very low, the treatment process is too simple, and the harmful substances in the waste gas are difficult to completely remove through one-time oxidation and one-time alkali washing. Meanwhile, the emission of fermentation tail gas in industrial production is extremely large, so that the number of oxidation towers, alkaline washing towers and water washing towers required for treating the tail gas is large, the occupied area of equipment is large, the construction, operation and maintenance costs are high, and the consumption of an oxidant and an alkali absorption liquid in the treatment process is also large.
At present, the report about the use of molecular sieve for waste gas treatment is that the molecular sieve is only combined with a thermal incinerator or a catalytic combustion device, no subsequent treatment process exists, the problem of insufficient catalysis or combustion is easily caused, and the molecular sieve is mainly applied to the field of waste gas treatment of spraying and tar processing only containing organic solvents. However, for fermentation waste gas with relatively complex components, it is difficult to achieve good purification effect by using these methods, and there is still harmful substance residue, which cannot completely meet the requirements of clean production and safe emission.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a purification treatment method of fermentation tail gas, which can thoroughly remove various harmful substances in the fermentation waste gas, realize standard emission, effectively reduce the usage amount of a circulating spray tower and absorption liquid, and reduce the waste gas treatment cost.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the method for purifying and treating the fermentation tail gas is characterized by comprising the following steps of:
a. pretreatment: the fermentation tail gas passes through a cyclone separator, a primary filter, a condenser and a heater in sequence;
b. treating a molecular sieve: b, filtering the gas treated in the step a through a molecular sieve, analyzing and concentrating harmful substances adsorbed on the molecular sieve by using high-temperature gas, and treating the gas which is not adsorbed by using an activated carbon treatment box;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation;
d. alkali washing: introducing the gas treated in the step c into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid;
e. secondary oxidation: d, introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidation absorption liquid;
f. washing with water: and e, introducing the gas treated in the step e into a water washing spray tower which is sprayed by water in a circulating manner, and discharging the gas at high altitude.
The technical scheme of the invention is further improved as follows: the primary filter is a plate-type primary filter, the relative humidity of the gas passing through the condenser is 35-50%, and the temperature of the gas passing through the heater is 20-40 ℃.
The technical scheme of the invention is further improved as follows: the molecular sieve is a honeycomb disc runner type molecular sieve, wherein the adsorption material used by the molecular sieve is composite high silicon with the aperture size of 0.3-1 nm.
The technical scheme of the invention is further improved as follows: the molecular sieve is divided into a treatment area, a regeneration area and a cooling area, the gas treated in the step a is filtered in the treatment area, the adsorbed harmful substances are desorbed in the regeneration area by high-temperature gas, the gas is cooled in the cooling area by low-temperature gas, and the volume of the high-temperature gas is 4-20% of the volume of the gas treated in the step a.
The technical scheme of the invention is further improved as follows: the temperature of the high-temperature gas is 150-250 ℃, and the temperature of the cooling zone is below 40 ℃ after the low-temperature gas is used for cooling.
The technical scheme of the invention is further improved as follows: and c, the low-temperature gas is the gas which is not adsorbed in the step b, and the gas which is not adsorbed is heated by the cooling zone and the regenerative heater to become the high-temperature gas.
The technical scheme of the invention is further improved as follows: the high-temperature catalytic oxidation device is heated to 240-320 ℃ by an electric heater, and the catalyst is a palladium-carbon catalyst.
The technical scheme of the invention is further improved as follows: and c, before the gas treated in the step c is introduced into an alkaline washing spray tower, the temperature of the gas is reduced to 35-45 ℃ through a heat exchanger.
The technical scheme of the invention is further improved as follows: the alkaline absorption liquid is a sodium hydroxide or potassium hydroxide solution with the mass percentage concentration of 5-20%.
The technical scheme of the invention is further improved as follows: the oxidizing absorption liquid is a sodium hypochlorite or potassium hypochlorite solution with the mass percentage concentration of 5-20%.
Due to the adoption of the technical scheme, the invention has the technical progress and the beneficial effects that:
the purification treatment method of the fermentation tail gas can thoroughly remove various harmful substances in the fermentation waste gas, realize standard emission, effectively reduce the use amount of the circulating spray tower and the absorption liquid, and reduce the waste gas treatment cost.
The pretreatment step of the invention can effectively solve the problem of adverse effects on equipment and treatment effect caused by unstable tail gas emission in the fermentation production process. The plate-type primary filter can play a certain buffering role on fermentation tail gas, so that the gas flow entering the molecular sieve is more stable without great fluctuation, thereby preventing the gas from generating high and low impact pressure on a plurality of devices including the molecular sieve at the back, reducing the problems of equipment damage and insufficient treatment, and particularly solving the problem of reduction of adsorption efficiency caused by sudden increase or reduction of adsorption resistance of the molecular sieve.
The primary filter used in the invention can play a good role in dedusting fermentation tail gas, and can capture dust particles with the diameter of more than 5 microns and various suspended particles in the gas, thereby preventing the molecular sieve from being polluted by dust, being beneficial to leading the molecular sieve to more effectively adsorb harmful substances, and reducing the cleaning and maintenance cost of the molecular sieve. Meanwhile, the plate-type primary filter has the advantages of low price, light weight, small resistance, high mechanical strength, good universality, compact structure, large dust holding capacity, convenience in cleaning and replacing filter materials and the like.
The cyclone separator in the pretreatment step can play a role in gas-liquid separation, effectively remove fermentation liquor possibly carried in fermentation tail gas and condensed water generated in the discharge process, and prevent liquid water from entering the molecular sieve to damage the service life of the molecular sieve or prevent adsorbates from having a competitive action to hinder the adsorption effect. The invention dehumidifies the gas treated by the cyclone separator through the condenser, condenses at low temperature to remove water vapor in the gas, and properly heats the condensed gas through the heater. When the relative humidity of the gas is controlled to be 35-50% and the temperature is within the range of 20-40 ℃, water cannot be condensed in the process of introducing the molecular sieve and meeting the molecular sieve, and excessive influence on the temperature of the molecular sieve in the treatment area cannot be caused.
The invention selects the hydrophobic molecular sieve with high silicon-aluminum ratio according to the characteristics of the particle diameter and the molecular polarity of various harmful substances in the fermentation waste gas, and has the characteristics of a net structure and selective adsorption. The used adsorbing material is a pore and cavity system formed by connecting silicon oxygen and aluminum tetrahedron through oxygen bridge bonds, the pore size is 0.3-1 nm, the pore size is matched with the size of molecules to be adsorbed, and the adsorbing material has high adsorption efficiency on fermentation tail gas. If the pore diameter is too large, the shape selection effect cannot be achieved, and if the pore diameter is too small, clogging is likely to occur.
The honeycomb runner used in the invention has a plurality of excellent characteristics, so that the molecular sieve has good adsorption performance on the fermentation tail gas. The specific surface area of the honeycomb structure can reach 2700m2/m3Above, can make fermentation tail gas and adsorption material in the molecular sieve fully contact, than the spherical molecular sieve mass transfer efficiency that the diameter is 3mm has improved more than one time, and windage resistance specific activity charcoal adsorbsThe device is much lower, so that the device has high purification efficiency.
Compared with the fixed bed type molecular sieve with intermittent switching, the disc rotating wheel type molecular sieve used by the invention has stronger operation continuity, and can continuously filter and regenerate the fermentation tail gas in cycles by carrying out adsorption, desorption and cooling in different areas of the disc and continuously rotating. The rotating speed of the molecular sieve used in the invention is properly matched with the adsorption speed, desorption speed and cooling speed of the fermentation tail gas, so that not only can a good purification effect be obtained, but also the treatment rate can be improved to the maximum extent and the energy consumption can be reduced. In addition, the molecular sieve also has the advantages of high operation stability, long service life, low maintenance cost, safety, reliability and the like.
According to the invention, after the pretreated gas is filtered and adsorbed on the molecular sieve in the molecular sieve treatment area, the high-temperature gas is used for desorption, the volume of the high-temperature gas is only 4-20% of that of the pretreated gas, harmful substances are concentrated in the high-temperature gas, and the problem of overlarge gas treatment amount caused by large discharge amount and low concentration of fermentation tail gas is effectively solved. Because the gas treatment capacity is greatly reduced, the tail gas treatment equipment required to be used in the subsequent steps is correspondingly reduced by times, so that the occupied area of the equipment, the construction investment and the operation and maintenance cost are obviously reduced, and the use amount and the energy consumption of the catalyst and the spray absorption liquid in the treatment process are also greatly reduced.
The temperature of the high-temperature gas used in the regeneration zone is 150-250 ℃, the adsorption force of the molecular sieve is weak at the temperature, and the high-temperature gas can completely carry out adsorbed substances when passing through the molecular sieve, so that the molecular sieve is regenerated. When the temperature is lower than the range, a good desorption effect cannot be achieved, and when the temperature is too high, excessive waste heat is generated on the molecular sieve, so that the molecular sieve is not completely cooled in a cooling area, the next adsorption effect is influenced, or the difficulty of the cooling process is increased. The molecular sieve is fully cooled in the cooling zone by low-temperature gas, so that the temperature of the molecular sieve is reduced to be below 40 ℃ before the molecular sieve enters the treatment zone, and the molecular sieve has strong adsorption force at low temperature, so that harmful substances in the fermentation tail gas can be well adsorbed in the treatment zone below 40 ℃.
The invention uses the unadsorbed gas after passing through the molecular sieve as the low-temperature gas for cooling the molecular sieve and the high-temperature gas for regenerating the molecular sieve, not only has good effect, but also makes the clean air fully utilized again, is very economical and convenient, and also meets the requirements of energy conservation and environmental protection. Because this gas has been handled through preliminary treatment and molecular sieve, consequently have the advantage that the temperature is low, humidity is little and clean, directly introduce cooling zone with the draught fan and can use to this gas discharge capacity is very big, can satisfy the needs of cooling molecular sieve completely. After the gas is cooled, the temperature of the gas can be increased, and after part of the gas is properly heated by a regeneration heater, the gas can become high-temperature gas which is continuously used for desorption and subsequent treatment processes of the molecular sieve in a regeneration area. The method can collect and recycle the heat energy released by the molecular sieve, and saves more energy than directly heating the outside cold air. If ordinary outside air is used as the cooling gas or the high-temperature gas, it is necessary to perform primary filtration to prevent contamination and damage to the molecular sieve, and it is also necessary to perform more temperature increase or decrease, thereby increasing the process complexity and the energy consumption cost. The unadsorbed gas is discharged after being treated by the activated carbon no matter the unadsorbed gas is used as the cooling molecular sieve, so the treatment cost is not increased, and the unadsorbed gas which is continuously used as the high-temperature desorption molecular sieve does not need to be treated by the activated carbon, so the treatment cost is reduced.
The catalytic oxidation step of the invention can oxidize and decompose most organic matters in the gas into carbon dioxide and water, and the removal rate of harmful substances is high and the residue is little. The catalyst used in the catalytic oxidation device is a palladium-carbon honeycomb ceramic catalyst, has a porous honeycomb structure, is small in fluid resistance and large in specific surface area, can be fully contacted with gas, improves the utilization rate and the reaction efficiency of the catalyst, can be repeatedly recycled, and saves the use cost of the catalyst. At a treatment capacity of 10000m3In the high-temperature catalytic device, when a rectangular block-shaped carbon honeycomb ceramic catalyst with the size of 1cm × 10 and 10cm × 5cm is used, the loading amount is 1400-1500 blocksThe temperature is 240-320 ℃, and compared with thermal incineration, catalytic reaction can take place at lower temperature, and the requirement on the device is lower, and the security is better. Besides flammable volatile organic compounds, the fermentation tail gas also contains other harmful substances which are difficult to be completely combusted, so that the fermentation tail gas cannot be completely removed by thermal incineration.
The gas after catalytic oxidation treatment is subjected to alkali washing, secondary oxidation and water washing treatment, so that a small amount of residual harmful substances which are not completely oxidized are further removed, and the requirements of clean emission and environmental protection can be better met. And the steps of alkaline washing, secondary oxidation and water washing are all processed by using a circulating spray tower, the absorption liquid can be fully contacted with the fermentation tail gas in a spraying mode, and the absorption liquid is circulated in the spray tower by using a circulating pump, so that the absorption liquid can be recycled. The circulating spray tower uses corrosion-resistant materials, preferably glass fiber reinforced plastics, and the used absorption liquid is a low-concentration and low-toxicity chemical solution, so that the circulating spray tower has the advantages of good absorption effect, low price, small environmental pollution and easiness in recovery and treatment.
The alkaline washing step of the invention aims at residual acid gas in the fermentation tail gas, and the acid gas can be completely absorbed and removed by circularly spraying the low-concentration alkaline solution. The oxidant used in the secondary oxidation step is stable under alkaline conditions, so that even if a small amount of alkaline absorption liquid in the previous step of treatment is carried in the fermentation tail gas, the oxidation performance of the fermentation tail gas cannot be affected, and the recovery treatment is very simple and convenient. The water washing step of the invention can dissolve and absorb the absorption liquid possibly carried by the fermentation tail gas in the previous treatment step by water, and finally completely remove various environmental pollutants in the fermentation tail gas before discharging.
After the fermentation tail gas is concentrated, the consumption of a spray tower and absorption liquid is greatly reduced, the pollution of chemical reagents to the environment is reduced, the floor area of treatment equipment is reduced, and the cost of equipment construction, operation and maintenance is saved. Compared with the existing fermentation tail gas treatment method, although the treatment steps are increased, the treatment difficulty and cost are reduced, the treatment efficiency is higher, and the purification effect is better from the comprehensive perspective.
Detailed Description
The following are some specific embodiments of the present invention, which are provided for further detailed description of the present invention, but not for limiting the scope of the present invention.
The invention relates to a fermentation tail gas purification treatment method, which comprises the following specific implementation steps:
a. pretreatment: carrying out gas-liquid separation on fermentation tail gas through a cyclone separator, then carrying out dust removal and buffering through a plate-type primary filter, then dehumidifying through a condenser to enable the relative humidity of the gas to reach 35-50%, and finally enabling the temperature of the gas to reach 20-40 ℃ through a heater to ensure that the moisture is not condensed any more;
b. treating a molecular sieve: a honeycomb-shaped disc runner type molecular sieve is used, composite high-silicon is used as an adsorptive material, the diameter of a runner is 245mm, the thickness of the runner is 40mm, the runner is divided into a treatment area, a regeneration area and a cooling area, the runner rotates in the direction of the treatment area, the regeneration area and the cooling area, and the rotating speed is 5-15 revolutions per hour. And (b) filtering the gas treated in the step (a) by the molecular sieve in a treatment zone, desorbing the adsorbed harmful substances by using high-temperature gas with the temperature of 150-250 ℃ in a regeneration zone, and cooling the gas which is not adsorbed to below 40 ℃ in a cooling zone. 4-20% of unadsorbed gas passes through a cooling zone and then is heated by a regenerative heater to become high-temperature gas, and the rest part of unadsorbed gas passes through the cooling zone and then is treated by an activated carbon treatment box and then is discharged;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation, heating the gas to 240-320 ℃ by using an electric heater, wherein the catalyst is a palladium-carbon catalyst;
d. alkali washing: c, reducing the temperature of the gas treated in the step c to 35-45 ℃ through a heat exchanger, and introducing the gas into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid, wherein the alkaline absorption liquid is sodium hydroxide or potassium hydroxide solution with the mass percentage concentration of 5-20%;
e. secondary oxidation: introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidative absorption liquid, wherein the oxidative absorption liquid is a sodium hypochlorite or potassium hypochlorite solution with the mass percentage concentration of 5-20%;
f. and e, introducing the gas treated in the step e into a water washing spray tower which is sprayed by water in a circulating way, and discharging the gas through a 25m high-altitude exhaust funnel.
Example 1
The specific implementation steps are as follows:
a. pretreatment: carrying out gas-liquid separation on the fermentation tail gas through a cyclone separator, then carrying out dust removal and buffering through a plate-type primary filter, then dehumidifying through a condenser to enable the relative humidity of the gas to reach 35%, and finally enabling the temperature of the gas to reach 20 ℃ through a heater to ensure that the moisture is not condensed any more;
b. treating a molecular sieve: a honeycomb-shaped disc runner type molecular sieve is used, composite high-silicon is used as an adsorptive material, the diameter of a runner is 245mm, the thickness of the runner is 40mm, the runner is divided into a treatment area, a regeneration area and a cooling area, the runner rotates in the direction from the treatment area to the regeneration area to the cooling area, and the rotating speed is 5 revolutions per hour. The molecular sieve filters the gas treated in step a in the treatment zone, desorbs the adsorbed harmful substances in the regeneration zone with high-temperature gas at 150 ℃, and cools to 10 ℃ in the cooling zone with non-adsorbed gas. After passing through the cooling zone, 20% of unadsorbed gas is heated by a regenerative heater to become high-temperature gas, and after passing through the cooling zone, the rest part of unadsorbed gas is treated by an activated carbon treatment box and then is discharged;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation, heating the gas to 240 ℃ by using an electric heater, wherein the catalyst is a palladium-carbon catalyst;
d. alkali washing: c, reducing the temperature of the gas treated in the step c to 35 ℃ through a heat exchanger, and introducing the gas into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid, wherein the alkaline absorption liquid is sodium hydroxide solution with the mass percentage concentration of 5%;
e. secondary oxidation: introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidative absorption liquid, wherein the oxidative absorption liquid is a sodium hypochlorite solution with the mass percentage concentration of 5%;
after the fermentation tail gas is purified and before being treated by the method in example 1, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odorous gases in the fermentation tail gas are respectively detected and compared with the discharge standard, and the detection results and the discharge standard are shown in the following table 1. Wherein the emission standard referred by the non-methane total hydrocarbon concentration and the odor gas concentration is the emission standard of penicillin pharmaceutical volatile organic compounds and odor characteristic pollutants (DB 13/2208-2015); the emission standard referred by the concentration and the emission rate of the volatile organic compounds is the industrial enterprise volatile organic compound emission control standard (DB 13/2208-2015).
TABLE 1
As can be seen from Table 1, after the treatment of the steps, the concentration and the discharge rate of volatile organic compounds, non-methane total hydrocarbons and odor gases in the fermentation tail gas are reduced by more than 90% compared with those before purification, and the concentration of each harmful substance is far lower than the discharge standard and can reach the discharge standard.
Example 2
The specific implementation steps are as follows:
a. pretreatment: the fermentation tail gas is firstly subjected to gas-liquid separation through a cyclone separator, then is subjected to dust removal and buffering through a plate-type primary filter, and is dehumidified through a condenser, so that the relative humidity of the gas reaches 50%, and finally, the temperature of the gas reaches 40 ℃ through a heater, and the moisture is guaranteed not to be condensed any more.
b. Treating a molecular sieve: a honeycomb-shaped disc runner type molecular sieve is used, composite high-silicon is used as an adsorptive material, the diameter of a runner is 245mm, the thickness of the runner is 40mm, the runner is divided into a treatment area, a regeneration area and a cooling area, the runner rotates in the direction from the treatment area to the regeneration area to the cooling area, and the rotating speed is 15 revolutions per hour. The molecular sieve filters the gas treated in step a in the treatment zone, desorbs the adsorbed harmful substances in the regeneration zone by using high-temperature gas with the temperature of 250 ℃, and cools to 38 ℃ in the cooling zone by using the unadsorbed gas. 4% of unadsorbed gas passes through the cooling zone and then is heated by a regenerative heater to become high-temperature gas, and the rest part of unadsorbed gas passes through the cooling zone and then is treated by an activated carbon treatment box and then is discharged;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation, heating the gas to 320 ℃ by using an electric heater, wherein the catalyst is a palladium-carbon catalyst;
d. alkali washing: c, reducing the temperature of the gas treated in the step c to 45 ℃ through a heat exchanger, and introducing the gas into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid, wherein the alkaline absorption liquid is potassium hydroxide solution with the mass percentage concentration of 20%;
e. secondary oxidation: introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidative absorption liquid, wherein the oxidative absorption liquid is a potassium hypochlorite solution with the mass percentage concentration of 20%;
after the fermentation tail gas is purified and before being treated by the method in example 2, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odorous gases in the fermentation tail gas are respectively detected and compared with the discharge standard, and the detection results and the discharge standard are shown in the following table 2. Wherein the emission standard referred by the non-methane total hydrocarbon concentration and the odor gas concentration is the emission standard of penicillin pharmaceutical volatile organic compounds and odor characteristic pollutants (DB 13/2208-2015); the emission standard referred by the concentration and the emission rate of the volatile organic compounds is the industrial enterprise volatile organic compound emission control standard (DB 13/2208-2015).
TABLE 2
As can be seen from Table 2, after the treatment of the steps, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odor gases in the fermentation tail gas are reduced by more than 90% compared with those before purification, and the concentrations of various harmful substances are far lower than the discharge standard and can reach the discharge standard.
Example 3
The specific implementation steps are as follows:
a. pretreatment: the fermentation tail gas is firstly subjected to gas-liquid separation through a cyclone separator, then is subjected to dust removal and buffering through a plate-type primary filter, and is dehumidified through a condenser, so that the relative humidity of the gas reaches 40%, and finally, the temperature of the gas reaches 25 ℃ through a heater, so that the moisture is not condensed any more.
b. Treating a molecular sieve: a honeycomb-shaped disc runner type molecular sieve is used, composite high-silicon is used as an adsorptive material, the diameter of a runner is 245mm, the thickness of the runner is 40mm, the runner is divided into a treatment area, a regeneration area and a cooling area, the runner rotates in the direction from the treatment area to the regeneration area to the cooling area, and the rotating speed is 8 revolutions per hour. The molecular sieve filters the gas treated in step a in the treatment zone, and the adsorbed harmful substances are desorbed by high-temperature gas with the temperature of 180 ℃ in the regeneration zone, and the gas which is not adsorbed is cooled to 15 ℃ in the cooling zone. 15% of unadsorbed gas passes through the cooling zone and then is heated by a regenerative heater to become high-temperature gas, and the rest part of unadsorbed gas passes through the cooling zone and then is treated by an activated carbon treatment box and then is discharged;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation, heating the gas to 280 ℃ by using an electric heater, wherein the catalyst is a palladium-carbon catalyst;
d. alkali washing: c, reducing the temperature of the gas treated in the step c to 40 ℃ through a heat exchanger, and introducing the gas into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid, wherein the alkaline absorption liquid is potassium hydroxide solution with the mass percentage concentration of 15%;
e. secondary oxidation: introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidative absorption liquid, wherein the oxidative absorption liquid is a sodium hypochlorite solution with the mass percentage concentration of 15%;
after the fermentation tail gas was purified and before the fermentation tail gas was treated by the method of example 3, the concentrations and emission rates of volatile organic compounds, non-methane total hydrocarbons and odorous gases were measured and compared with emission standards, and the results and emission standards are shown in table 3 below. Wherein the emission standard referred by the non-methane total hydrocarbon concentration and the odor gas concentration is the emission standard of penicillin pharmaceutical volatile organic compounds and odor characteristic pollutants (DB 13/2208-2015); the emission standard referred by the concentration and the emission rate of the volatile organic compounds is the industrial enterprise volatile organic compound emission control standard (DB 13/2208-2015).
TABLE 3
As can be seen from Table 3, after the treatment of the steps, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odor gases in the fermentation tail gas are reduced by more than 90% compared with those before purification, and the concentrations of various harmful substances are far lower than the discharge standard and can reach the discharge standard.
Example 4
The specific implementation steps are as follows:
a. pretreatment: the fermentation tail gas is firstly subjected to gas-liquid separation through a cyclone separator, then is subjected to dust removal and buffering through a plate-type primary filter, and then is dehumidified through a condenser, so that the relative humidity of the gas reaches 45%, and finally, the temperature of the gas reaches 35 ℃ through a heater, and the moisture is guaranteed not to be condensed any more.
b. Treating a molecular sieve: a honeycomb-shaped disc runner type molecular sieve is used, composite high-silicon is used as an adsorptive material, the diameter of a runner is 245mm, the thickness of the runner is 40mm, the runner is divided into a treatment area, a regeneration area and a cooling area, the runner rotates in the direction from the treatment area to the regeneration area to the cooling area, and the rotating speed is 12 revolutions per hour. The molecular sieve filters the gas treated in step a in the treatment zone, desorbs the adsorbed harmful substances in the regeneration zone by using high-temperature gas with the temperature of 220 ℃, and cools to 30 ℃ in the cooling zone by using the unadsorbed gas. After passing through the cooling zone, 10% of unadsorbed gas is heated by a regenerative heater to become high-temperature gas, and after passing through the cooling zone, the rest part of unadsorbed gas is treated by an activated carbon treatment box and then is discharged;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation, heating the gas to 300 ℃ by using an electric heater, wherein the catalyst is a palladium-carbon catalyst;
d. alkali washing: c, reducing the temperature of the gas treated in the step c to 38 ℃ through a heat exchanger, and introducing the gas into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid, wherein the alkaline absorption liquid is a sodium hydroxide solution with the mass percentage concentration of 10%;
e. secondary oxidation: introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidative absorption liquid, wherein the oxidative absorption liquid is a sodium hypochlorite solution with the mass percentage concentration of 10%;
after the fermentation tail gas is purified and before treated by the method of example 4, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odorous gases in the fermentation tail gas are respectively detected and compared with the discharge standards, and the detection results and the discharge standards are shown in the following table 4. Wherein the emission standard referred by the non-methane total hydrocarbon concentration and the odor gas concentration is the emission standard of penicillin pharmaceutical volatile organic compounds and odor characteristic pollutants (DB 13/2208-2015); the emission standard referred by the concentration and the emission rate of the volatile organic compounds is the industrial enterprise volatile organic compound emission control standard (DB 13/2208-2015).
TABLE 4
As can be seen from Table 4, after the treatment of the steps, the concentrations and the discharge rates of volatile organic compounds, non-methane total hydrocarbons and odor gases in the fermentation tail gas are reduced by more than 90% compared with those before purification, and the concentrations of various harmful substances are far lower than the discharge standard and can reach the discharge standard.
Claims (4)
1. A fermentation tail gas purification treatment method is characterized by comprising the following steps:
a. pretreatment: the fermentation tail gas passes through a cyclone separator, a primary filter, a condenser and a heater in sequence; the primary filter is a plate-type primary filter, the relative humidity of the gas passing through the condenser is 35-50%, and the temperature of the gas passing through the heater is 20-40 ℃;
b. treating a molecular sieve: b, filtering the gas treated in the step a through a molecular sieve, analyzing and concentrating harmful substances adsorbed on the molecular sieve by using high-temperature gas, and treating the gas which is not adsorbed by using an activated carbon treatment box; the molecular sieve is divided into a treatment area, a regeneration area and a cooling area, the gas treated in the step a is filtered in the treatment area, the adsorbed harmful substances are desorbed in the regeneration area by high-temperature gas, the molecular sieve is cooled by low-temperature gas in the cooling area, and the volume of the high-temperature gas is 4-20% of that of the gas treated in the step a; the low-temperature gas is unadsorbed gas, and the unadsorbed gas becomes the high-temperature gas after being heated by the cooling zone and the regenerative heater; the molecular sieve is a honeycomb disc runner type molecular sieve, wherein the used adsorptive material is composite high silicon with the aperture size of 0.3-1 nm;
c. catalytic oxidation: b, introducing the gas treated in the step b into a high-temperature catalytic oxidation device containing a catalyst for catalytic oxidation; the high-temperature catalytic oxidation device is heated to 240-320 ℃ by an electric heater, and the catalyst is a palladium-carbon catalyst;
d. alkali washing: introducing the gas treated in the step c into an alkaline washing spray tower circularly sprayed by alkaline absorption liquid;
e. secondary oxidation: d, introducing the gas treated in the step d into an oxidation spray tower circularly sprayed by using an oxidation absorption liquid;
f. washing with water: e, introducing the gas treated in the step e into a water washing spray tower which is sprayed by water in a circulating way, and discharging the gas at high altitude;
wherein the temperature of the high-temperature gas is 150-250 ℃, and the temperature of the cooling zone is below 40 ℃ after being cooled by the low-temperature gas; the composite high silicon is formed by connecting silicon oxygen and aluminum tetrahedron through oxygen bridge bonds to form a pore canal and cavity system.
2. The fermentation tail gas purification treatment method according to claim 1, characterized in that: and c, before the gas treated in the step c is introduced into an alkaline washing spray tower, the temperature of the gas is reduced to 35-50 ℃ through a heat exchanger.
3. The fermentation tail gas purification treatment method according to claim 1, characterized in that: the alkaline absorption liquid is a sodium hydroxide or potassium hydroxide solution with the mass percentage concentration of 5-20%.
4. The fermentation tail gas purification treatment method according to claim 1, characterized in that: the oxidizing absorption liquid is a sodium hypochlorite or potassium hypochlorite solution with the mass percentage concentration of 5-20%.
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