CN108837682B - Composite eluting agent combination, application thereof and fermentation tail gas treatment method adopting composite eluting agent combination - Google Patents
Composite eluting agent combination, application thereof and fermentation tail gas treatment method adopting composite eluting agent combination Download PDFInfo
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- CN108837682B CN108837682B CN201810694555.9A CN201810694555A CN108837682B CN 108837682 B CN108837682 B CN 108837682B CN 201810694555 A CN201810694555 A CN 201810694555A CN 108837682 B CN108837682 B CN 108837682B
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D53/77—Liquid phase processes
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- 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
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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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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Abstract
The composite eluent combination for treating the fermentation tail gas comprises a first-stage eluent and a second-stage eluent, wherein the first-stage eluent comprises a compound medicament of sodium hydroxide or sodium carbonate and sodium hypochlorite, and the second-stage eluent comprises hydrochloric acid and hydrogen peroxide. The application comprises the following steps: and adding the first-stage eluting agent into the first-stage spray tower, adding the second-stage eluting agent into the second-stage spray tower, opening a reflux pump to fully elute the fermentation waste gas, and greatly relieving the peculiar smell of the tail gas. The removal rate of the odor substances can reach 78%, the original spray tower structure is not required to be changed, the construction cost and the operation cost are saved, and the method has good application and popularization prospects.
Description
Technical Field
The invention belongs to the technical field of waste gas purification treatment, and particularly relates to a composite eluent composition, application thereof and a fermentation tail gas treatment method adopting the same.
Background
The main components of the fermentation waste gas are water vapor and air, but the fermentation waste gas is mixed with trace nitrogen oxides, sulfides, volatile organic compounds, non-methane total hydrocarbons and other peculiar smell substances, the direct emission of the peculiar smell substances pollutes the air of the factory boundary, and meanwhile, the peculiar smell air also influences the physical and mental health of surrounding residents to a certain extent. With the stricter tail gas emission standards in the pharmaceutical industry, higher requirements are put forward on the odor concentration control technology of fermentation tail gas.
The method for treating the peculiar smell of the fermentation tail gas mainly comprises chemical leaching, activated carbon adsorption, ozone oxidation, a microorganism deodorization method and the like, and each technology has certain limitation. For example, the combination of the traditional acidic or alkaline eluting agent and clear water has strong universality, but weak pertinence and low odor removal rate; the activated carbon adsorption has high removal rate in a short time, but the failure is quick, and the removal rate changes greatly after a period of time; the microbial deodorization method has the advantages of long strain screening period, large equipment volume, high early investment and high removal rate influenced by the microbial condition.
In consideration of economic cost, technical level, standard requirements and the like, spray washing is one of the most widely applied technologies in the fermentation tail gas treatment in the pharmaceutical industry of China at present, and reasonable use of spray liquid directly determines the treatment effect.
Disclosure of Invention
In view of the above, the present invention provides a composite eluting agent for treating fermentation tail gas, so as to at least partially solve at least one of the above technical problems.
To achieve the above object, as one aspect of the present invention, there is provided a composite eluent combination including a first-stage eluent for first-stage elution and a second-stage eluent for second-stage elution; wherein, the first-stage eluting agent comprises sodium hydroxide and sodium carbonate, and sodium hypochlorite; the second stage eluent comprises hydrochloric acid and hydrogen peroxide.
As another aspect of the invention, the invention also provides the application of the composite eluting agent combination in fermentation tail gas treatment.
As another aspect of the present invention, there is provided a method for treating fermentation tail gas, comprising the steps of:
adding a first-stage eluting agent into the first-stage spray tower, adding a second-stage eluting agent into the second-stage spray tower, and opening a reflux pump to sufficiently elute the fermentation waste gas to be treated;
wherein the first stage eluent and the second stage eluent are from a composite eluent combination as described above.
Compared with the prior art, the invention has the beneficial effects that:
(1) the composite eluting agent disclosed by the invention is simple in preparation method, wide in raw material source and low in cost, can realize quick and efficient chemical reaction and physical adsorption of peculiar smell substances such as nitric oxide, sulfide and the like, obviously reduces the peculiar smell of the tail gas as a whole, and lays the foundation of the first step for zero emission of fermentation tail gas;
(2) the spray tower device is simple and easy to maintain, can utilize the existing field and facilities, does not need to expand and upgrade a factory, and has the potential of large-scale popularization;
(3) the concentration value of the tail gas odor treated by the method is obviously reduced, and the removal rate of the odor substances reaches 78%;
(4) the invention is particularly suitable for treating antibiotic fermentation tail gas, such as tylosin fermentation tail gas.
Drawings
FIG. 1 is a schematic diagram of the structure of a two-stage vertical packed absorption column of the present invention.
In the above figures, the reference numerals have the following meanings:
1-a first-stage tower; 2-a first circulation pump; 3-a secondary column; 4-second circulation pump.
Detailed Description
In order that the objects, technical solutions and advantages of the present invention will become more apparent, the present invention will be further described in detail with reference to the accompanying drawings in conjunction with the following specific embodiments.
The invention discloses a composite eluent combination for treating fermentation tail gas, which comprises a first-stage eluent and a second-stage eluent, wherein the first-stage eluent comprises sodium hydroxide and sodium carbonate, sodium hypochlorite is added, and the second-stage eluent comprises hydrochloric acid and hydrogen peroxide.
Preferably, sodium hydroxide, sodium carbonate, sodium hypochlorite, hydrochloric acid, hydrogen peroxide are all technical grade.
Preferably, the mass concentration of the sodium hypochlorite in the first-stage eluting agent is 0.05-0.5%.
Preferably, the pH of the sodium hydroxide in the first stage eluent is 12 + -1, or the pH of the sodium carbonate in the first stage eluent is 11.78 + -1.
Preferably, the mass concentration of the hydrogen peroxide in the second-stage eluting agent is 1-5%.
Preferably, the pH value of the hydrochloric acid in the second-stage eluting agent is 3-4.
The invention also discloses application of the composite eluent composition in treatment of fermentation tail gas, in particular to application of antibiotic fermentation tail gas.
The application specifically comprises the following steps: and adding the first-stage eluting agent into the first-stage spray tower, adding the second-stage eluting agent into the second-stage spray tower, opening the reflux pump to fully elute the fermentation waste gas, and greatly relieving the peculiar smell of the tail gas. Through detection, the removal rate of the odor substances can reach 78%. The application does not need to change the original spray tower structure, saves the construction cost and the operation cost, and has good application and popularization prospects.
Preferably, the first stage eluent 1,000kg treats 200,000 + -1,000 m3Treating fermentation tail gas with 200,000 + -1,000 m with 1,000kg second stage eluent3Fermentation tail gas after the first-stage eluting agent treatment.
The invention also discloses a method for treating the fermentation tail gas, which comprises the following steps:
adding a first-stage eluting agent into the first-stage spray tower, adding a second-stage eluting agent into the second-stage spray tower, and opening a reflux pump to sufficiently elute the fermentation waste gas;
wherein the first stage eluent and the second stage eluent are from a composite eluent combination as described above.
Preferably, the first stage eluent 1,000kg treats about 200,000. + -. 1,000m3Treating fermentation tail gas with 1,000kg of second stage eluting agent at 200,000 + -1,000 m3Fermentation tail gas after the first-stage eluting agent treatment.
In a specific embodiment, the composite eluent composition for treating fermentation tail gas comprises a first-stage eluent and a second-stage eluent, wherein the first-stage eluent comprises sodium hydroxide or sodium carbonate and sodium hypochlorite, the second-stage eluent comprises hydrochloric acid and hydrogen peroxide, and the sodium hydroxide, the sodium carbonate, the sodium hypochlorite, the hydrochloric acid and the hydrogen peroxide are all industrial-grade. The mass concentration of sodium hypochlorite in the first-stage eluting agent is 0.05-0.5%, and the pH value is 12 +/-1; the mass concentration of hydrogen peroxide in the second-stage eluting agent is 1% -5%, and the pH value is 3-4.
The sodium hypochlorite in the first-stage eluting agent has the following functions: reacting with carbon dioxide in tail gas to generate hypochlorous acid, and reacting the hypochlorous acid with strong oxidizing property with nitric oxide molecules and sulfide molecules to generate acid radical ions and salts which are easy to dissolve in water; the sodium hydroxide or sodium carbonate in the first-stage eluting agent has the following functions: maintaining alkaline condition to make sodium hypochlorite stable and not decomposed before use; the hydrogen peroxide and hydrochloric acid in the second-stage eluting agent have the following functions: under the weak acidic condition, the ionization balance of the hydrogen peroxide is shifted to the left, and the hydrogen peroxide molecule has stronger oxidability, so that the reducing compound molecules containing sulfur and nitrogen with low odor threshold can be oxidized, and the whole odor degree is greatly reduced. The second-stage eluting agent further absorbs and reacts the tail gas leached by the first stage, so that the treatment effect of the second-stage eluting on the peculiar smell of the fermentation tail gas is controlled at a lower level.
The composite eluting agent combination for treating the fermentation tail gas can be suitable for various spray towers. Taking a two-stage vertical packing absorption tower as an example, as shown in fig. 1, when fermentation tail gas is treated, a first-stage eluent is circulated in a first-stage tower 1 by a first circulating pump 2, a second-stage eluent is circulated in a second-stage tower 3 by a second circulating pump 4, and the maximum treatment capacity of 1,000kg of the first-stage eluent or the second-stage eluent is 200,000 +/-1,000 m3And (4) calculating the change time of the eluent according to the current gas flow of the fermentation tail gas so as to ensure the treatment effect.
The technical solution of the present invention is further illustrated by the following specific examples.
Example 1
The composite eluting agent combination for treating the fermentation tail gas comprises a first-stage eluting agent and a second-stage eluting agent. The first-stage eluting agent is NaOH or Na2CO3And NaClO, the second-stage eluting agent is HCl and H2O2. Wherein the chemical substances are all industrial grade.
The method for treating tylosin fermentation tail gas by using the composite eluting agent comprises the following steps.
Pumping the first-stage eluting agent into a liquid storage tank of a first-stage vertical filler absorption tower, wherein the total mass of liquid is about 10,000kg, the concentration of NaOH is 0.01mol/L, the pH value is 12, and the mass concentration of NaClO is about 0.2%; pumping the second-stage eluting agent into a liquid storage tank of a second-stage vertical packing absorption tower, wherein the total mass of the liquid is about 10,000kg, the molar concentration of HCl is 0.001mol/L, and the pH value is 3. H2O2Is about 2 percent, and the total air input of the fermentation tail gas in the two-stage reactor is 45,000m3And starting a circulating pump to fully mix the eluting agent and the fermentation tail gas.
The treatment time is 30 minutesPortable clock equipment (VOCs and odor concentration) detection, VOCs is from 26.5mg/m3Down to about 8.2mg/m3The removal rate is 69%; the odor concentration value is reduced from 4200 to 1400, and the odor treatment rate is about 67%.
Example 2
The composite eluting agent combination for treating the fermentation tail gas comprises a first-stage eluting agent and a second-stage eluting agent. The first-stage eluting agent is NaOH or Na2CO3And NaClO, the second-stage eluting agent is HCl and H2O2. Wherein the chemical substances are all industrial grade.
The method for treating the erythromycin fermentation tail gas by using the composite eluting agent comprises the following steps.
Pumping the first-stage eluting agent into a liquid storage tank of a first-stage vertical filler absorption tower, wherein the total mass of liquid is about 20,000kg, the concentration of NaOH is 0.01mol/L, the pH value is 12, and the mass concentration of NaClO is about 0.5%; pumping the second-stage eluting agent into a liquid storage tank of a second-stage vertical filler absorption tower, wherein the total mass of liquid is about 20,000kg, the molar concentration of HCl is 0.001mol/L, and the pH value is 3; h2O2Is about 5 percent, and the total air input of the fermentation tail gas in the two-stage reactor is 30,000m3And starting a circulating pump to fully mix the eluting agent and the fermentation tail gas.
The treatment time is 30 minutes, and the treatment time is detected by a portable device (VOCs and odor concentration), and the VOCs is 21mg/m3Down to about 3.1mg/m3The removal rate is 85 percent; the odor concentration value is reduced from 23000 to about 4210, and the odor treatment rate is about 82%.
Example 3
The composite eluting agent combination for treating the fermentation tail gas comprises a first-stage eluting agent and a second-stage eluting agent. The first-stage eluting agent is NaOH or Na2CO3And NaClO, the second-stage eluting agent is HCl and H2O2. Wherein the chemical substances are all industrial grade.
The method for treating tiamulin fermentation tail gas by using the composite eluting agent comprises the following steps.
Pumping the first-stage eluting agent into a liquid storage tank of a first-stage vertical packing absorption tower, wherein the total mass of the liquid is about 10,000kg, and the NaO content isThe H concentration is 0.01mol/L, the pH value is 12, and the mass concentration of NaClO is about 0.1%; pumping the second-stage eluting agent into a liquid storage tank of a second-stage vertical packing absorption tower, wherein the total mass of the liquid is about 10,000kg, the molar concentration of HCl is 0.0001mol/L, and the pH value is 4; h2O2Is about 1 percent, and the total air input of the fermentation tail gas in the two-stage reactor is 23,000m3And starting a circulating pump to fully mix the eluting agent and the fermentation tail gas.
The treatment time is 30 minutes, and the treatment time is measured by a portable device (VOCs and odor concentration), and the VOCs is 9.3mg/m3Down to about 1.8mg/m3The removal rate is 80 percent; the odor concentration value is reduced from 1700 to about 420, and the odor treatment rate is about 75%.
The compound eluting agent combination recited in the present invention is not limited to the above embodiments, the specific implementation method determines the use concentration according to different fermentation types and different gas volumes, the method can be used for different fermentation tail gases, and the specific implementation is not illustrated herein.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention and are not intended to limit the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A composite eluting agent combination comprises a first-stage eluting agent for first-stage eluting and a second-stage eluting agent for second-stage eluting, wherein the first-stage eluting agent comprises sodium hydroxide and sodium carbonate, sodium hypochlorite is added, and the second-stage eluting agent comprises hydrochloric acid and hydrogen peroxide;
the mass concentration of sodium hypochlorite in the first-stage eluting agent is 0.05-0.5%;
the molar concentration of sodium hydroxide in the first-stage eluting agent is 0.01 +/-0.005 mol/L, or the molar concentration of sodium carbonate in the first-stage eluting agent is 0.02 +/-0.01 mol/L;
the pH value of the first-stage eluting agent is 12 +/-1;
the mass concentration of the hydrogen peroxide in the second-stage eluting agent is 1-5%;
the molar concentration of hydrochloric acid in the second-stage eluting agent is 0.0001-0.001 mol/L;
the pH value of the second-stage eluting agent is 3-4;
wherein the compound eluting agent is used for treating fermentation tail gas; the fermentation tail gas is antibiotic fermentation tail gas; the fermentation tail gas comprises carbon dioxide, nitrogen oxide molecules and sulfide molecules; the removal rate of the odor substances in the fermentation tail gas is more than or equal to 78%.
2. The composite eluent combination of claim 1, wherein the sodium hydroxide, sodium carbonate, sodium hypochlorite, hydrochloric acid, and hydrogen peroxide are all technical grade.
3. Use of a combination of composite eluents according to claim 1 or 2 in the treatment of fermentation off-gas.
4. The application according to claim 3, characterized in that it comprises in particular the steps of: and adding the first-stage eluting agent into the first-stage spray tower, adding the second-stage eluting agent into the second-stage spray tower, and starting a reflux pump to sufficiently elute the fermentation tail gas to be treated.
5. The use of claim 4, wherein 1,000kg of said first stage eluent can treat 200,000 ± 10,000m3Fermentation tail gas, wherein 1,000kg of the second-stage eluting agent is treated with 200,000 +/-10,000 m3And (3) fermentation tail gas treated by the first-stage eluting agent.
6. The method for treating the fermentation tail gas is characterized by comprising the following steps of:
adding a first-stage eluting agent into the first-stage spray tower, adding a second-stage eluting agent into the second-stage spray tower, and opening a reflux pump to sufficiently elute the fermentation waste gas to be treated;
wherein the first stage eluent and the second stage eluent are from a composite eluent combination as claimed in claim 1 or 2.
7. The process of claim 6 wherein said first stage eluent is 1,000kg processed 200,000 ± 10,000m3Treating fermentation tail gas with 1,000kg of second stage eluting agent at 200,000 + -10,000 m3And (3) fermentation tail gas treated by the first-stage eluting agent.
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