CN110981003B - Secondary value-added utilization method of amino acid fermentation wastewater - Google Patents
Secondary value-added utilization method of amino acid fermentation wastewater Download PDFInfo
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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Abstract
The invention belongs to the technical field of biological environmental protection, and discloses a method for secondary value-added utilization of amino acid fermentation wastewater, which comprises the following steps: step 1) preparing modified montmorillonite, step 2) treating fermentation wastewater, and step 3) preparing a fertilizer. Fermentation wastewater can be used in fertilizer preparation, but the wastewater cannot be fully and effectively utilized; the invention purifies the waste water by adsorption, and the waste water is comprehensively utilized after being discharged; the waste mycoprotein combines part of fermentation wastewater and waste adsorbent after wastewater treatment, so that fertilizer can be prepared, the additional value of products is improved, the requirements of resource conservation and enterprise competitiveness are met, and the win-win situation is realized in both economic benefit and ecological environment, so that the coordination and unification of economic benefit, environmental benefit and social benefit are realized.
Description
Technical Field
The invention belongs to the technical field of biological environmental protection, and particularly relates to a secondary value-added utilization method of amino acid fermentation wastewater.
Background
The management of the circular economy mode is a key problem of the sustainable development of enterprises, and not only is the management directly related to social problems of enterprise production, economic development and the like, but also the management is related to the environmental problems which are increasingly concerned by people. The circular economy is an economic development mode which takes the high-efficiency utilization and the circular utilization of resources as the core, takes the reduction, the reutilization and the recycling as the principles and takes the low consumption, the low emission and the high efficiency as the basic characteristics, thereby utilizing the resources to the maximum extent and protecting the environment and being in line with the sustainable development concept. Enterprises can reasonably and effectively solve the problems of optimal configuration of various production resources and reutilization of byproduct resources by establishing a circular economy system. The production process of biological fermentation products produces a large amount of high-concentration fermentation waste liquid in the production process, the waste liquid is discharged after amino acid is extracted from fermentation liquor by the modes of centrifugal sedimentation, membrane filtration and the like, the waste liquid is rich in suspended solid matters of amino acid, thallus, protein and the like, various inorganic salts, organic acid, biotin, reducing sugar and the like, and the amino acid fermentation waste liquid can cause great influence on the environment no matter the waste liquid is directly discharged or is simply treated and then discharged.
The fermentation waste liquid is the waste liquid discharged after amino acid is extracted from fermentation liquid in the production process of amino acid, the waste liquid is industrial waste water with high COD, high sulfur, high ammonia nitrogen and high thallus content and low pH value, and the amino acid fermentation waste liquid can cause great influence on the environment no matter the industrial waste water is directly discharged or is discharged after being simply treated. Great amount of research is carried out on the treatment problem of the fermentation waste liquid in colleges and universities, scientific research institutions and monosodium glutamate production enterprises, and various treatment technologies and methods are provided according to the characteristics of the fermentation waste liquid, wherein the treatment technologies comprise the steps of producing biological pesticides by using the amino acid fermentation waste liquid, forming biomass hydrogen energy, culturing feed protein and the like, and the process for culturing the unicellular yeast protein by using the fermentation waste liquid is relatively mature.
The prior patent art of the applicant has conducted a great deal of research on fermentation wastewater. However, part of the research uses microbial preparations with higher cost and complex process, and the waste adsorbent generated in part of the research cannot be effectively utilized, so that the wastewater treatment process needs to be subsequently improved to achieve the purpose of comprehensive utilization.
Disclosure of Invention
The invention aims to provide a method for secondary value-added utilization of amino acid fermentation wastewater, which aims at overcoming the defects of the prior art.
In order to achieve the purpose of the invention, the following technical scheme is adopted.
A method for secondary value-added utilization of amino acid fermentation wastewater comprises the following steps: step 1) preparing modified montmorillonite, step 2) treating fermentation wastewater, and step 3) preparing a fertilizer.
Specifically, the method comprises the following steps:
step 1) preparation of modified montmorillonite: crushing montmorillonite powder, sieving with a 50-mesh sieve, collecting undersize, drying and dehydrating at 100 deg.C for 30-60min, taking out montmorillonite powder, and mixing with 1 g: adding 1-3ml of citric acid aqueous solution, performing soaking modification treatment at 60 deg.C for 60min under heat preservation condition, adding nanometer activated carbon, increasing reaction temperature to 70 deg.C, centrifuging at 500rpm for 3min under heat preservation condition, collecting precipitate, and oven drying at low temperature to obtain modified montmorillonite;
step 2) fermentation wastewater treatment: allowing glutamic acid fermentation wastewater to enter a sedimentation tank, naturally settling, performing solid-liquid separation to obtain sediment and supernatant, discharging the supernatant into a treatment tank, adjusting the pH to 6-7, adding modified montmorillonite for treatment, filtering, collecting waste modified montmorillonite, and discharging liquid for field irrigation or boiler cooling;
step 3) preparing a fertilizer: adding waste modified montmorillonite, glutamic acid fermentation waste mycoprotein and glutamic acid fermentation wastewater into a stirring tank, stirring at 500rpm for 15-30min, then feeding into a reaction tank, controlling the temperature of the reaction tank at 100 ℃, reacting for 30-60min, and then cooling to room temperature to obtain a mixed feed liquid; and (3) uniformly mixing the mixed feed liquid, monoammonium phosphate and urea, then adding the mixture into a double-screw granulator for granulation, and drying to obtain the fertilizer.
Preferably, the mass fraction of the citric acid aqueous solution is 5-15%.
Preferably, the addition amount of the nano activated carbon is 20-40% by mass of the montmorillonite powder.
Preferably, in the step 2), the addition amount of the modified montmorillonite is 0.05-0.1% by weight, and the treatment time is 24-48 h.
Preferably, in the step 3), the waste modified montmorillonite, the glutamic acid fermentation waste mycoprotein and the glutamic acid fermentation wastewater are added according to the proportion of 3-5kg:1-2kg: 5-8L.
Preferably, in the step 3), the mixed material liquid, the monoammonium phosphate and the urea are uniformly mixed according to the mass ratio of 3-5:1-2: 1-2.
More preferably, the mass fraction of the aqueous citric acid solution is 10%.
More preferably, the addition amount of the nano activated carbon is 30% by mass of the montmorillonite powder.
Compared with the prior art, the invention has the advantages that the following aspects are mainly included but not limited:
wastewater can be used in fertilizer preparation, but the wastewater cannot be fully and effectively utilized; the invention purifies the waste water by adsorption, and after the waste water is discharged, the waste water is irrigated in farmlands or is comprehensively utilized by other means, such as cooling a boiler; the mycoprotein combines part of fermentation wastewater and waste adsorbent after wastewater treatment, can be used for preparing fertilizer, improves the added value of products, meets the requirements of resource conservation and enterprise competitiveness, realizes win-win effect on economic benefit and ecological environment, and realizes coordination and unification of economic benefit, environmental benefit and social benefit.
The invention modifies the montmorillonite, and the adsorption effect is greatly improved; montmorillonite has strong cation exchange capacity, during the acidification process of montmorillonite, hydrogen ions firstly displace metal cations in interlaminar regions, the special performance of the hydrogen ions can adsorb organic matters, the montmorillonite is negatively charged and mutually exclusive along with the partial outflow of the metal cations, so that the specific surface area is increased, and a large number of broken bonds are formed due to the removal of partial hydroxyl groups, so that the activity is enhanced; compared with sulfuric acid, the citric acid treatment condition is mild, and can not cause great damage to active groups on montmorillonite, so that the original structure of montmorillonite is changed; the interlayer spacing of the montmorillonite is improved by citric acid modified acidification treatment.
Under the condition of citric acid and a certain temperature, metal cations on the montmorillonite can generate copolymerization and complexation reaction with inorganic anions on the nano activated carbon, such as carboxyl and other groups, so that a deposition effect is formed, and the nano activated carbon is deposited on the surface of the montmorillonite to form a flocculating constituent; the nano activated carbon is attached to the surface of montmorillonite, has good adsorption performance, and can also enrich microorganisms in wastewater to be used as an attachment carrier of the microorganisms.
The nano activated carbon and the montmorillonite are skillfully complexed together to prepare the modified montmorillonite, and different adsorption mechanisms are adopted, so that the nano activated carbon and the montmorillonite can be mutually cooperated to efficiently remove pollutants, the treatment time is shortened, and the sewage treatment efficiency is improved.
Drawings
FIG. 1: the removal rate of each main pollutant by different adsorbent types;
FIG. 2: the effect of different acid treated montmorillonite on ammonia nitrogen removal;
FIG. 3: the influence of the addition amount of the activated carbon on the ammonia nitrogen removal rate of the modified montmorillonite.
Detailed Description
In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the present application will be clearly and completely described below with reference to specific embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for secondary value-added utilization of amino acid fermentation wastewater comprises the following steps:
preparing glutamic acid fermentation liquor by utilizing corynebacterium glutamicum fermentation, centrifuging the fermentation liquor, collecting waste mycoprotein and filtrate, preparing glutamic acid from the filtrate according to a conventional extraction process, and reserving fermentation wastewater generated in the extraction process for later use;
1) preparing modified montmorillonite: crushing montmorillonite powder, sieving with a 50-mesh sieve, collecting undersize, placing in a drying container at 100 ℃ for drying and dehydrating for 30min, taking out the montmorillonite powder, and mixing the montmorillonite powder with the rest raw materials in a weight ratio of 1 g: adding 10% citric acid aqueous solution into 2ml of the mixture, soaking and modifying at 60 deg.C for 60min, adding 30% montmorillonite powder (dehydrated montmorillonite powder) nanometer activated carbon, heating to 70 deg.C for 60min, centrifuging at 500rpm for 3min, collecting precipitate, and oven drying at low temperature to obtain modified montmorillonite;
2) allowing glutamic acid fermentation wastewater to enter a sedimentation tank, naturally settling, performing solid-liquid separation to obtain sediment and supernatant, discharging the supernatant into a treatment tank, adjusting the pH to 6.5, adding 0.08% of modified montmorillonite for treatment for 36h, filtering, collecting waste modified montmorillonite, and discharging liquid for agricultural irrigation or boiler cooling;
3) adding the waste modified montmorillonite, the waste mycoprotein and the fermentation wastewater into a stirring tank according to the proportion of 3kg to 1kg to 5L, stirring for 15min at 500rpm, then entering a reaction tank, controlling the temperature of the reaction tank to be 100 ℃, reacting for 30min, and then cooling to room temperature to obtain a mixed feed liquid; uniformly mixing the mixed feed liquid, monoammonium phosphate and urea according to the mass ratio of 4:1:1, adding the mixture into a double-screw granulator for granulation, and drying to obtain the fertilizer.
Example 2
A method for secondary value-added utilization of amino acid fermentation wastewater comprises the following steps:
preparing glutamic acid fermentation liquor by utilizing corynebacterium glutamicum fermentation, centrifuging the fermentation liquor, collecting waste mycoprotein and filtrate, preparing glutamic acid from the filtrate according to a conventional extraction process, and reserving fermentation wastewater generated in the extraction process for later use;
1) preparing modified montmorillonite: crushing montmorillonite powder, sieving with a 50-mesh sieve, collecting undersize, placing in a drying container at 100 ℃ for drying and dehydrating for 30min, taking out the montmorillonite powder, and mixing the montmorillonite powder with the rest raw materials in a weight ratio of 1 g: adding 10% citric acid aqueous solution into 2ml of the mixture, soaking and modifying at 60 deg.C for 60min, adding 30% montmorillonite powder by mass of nano activated carbon, reacting at 70 deg.C for 60min, centrifuging at 500rpm for 3min, collecting precipitate, and oven drying at low temperature to obtain modified montmorillonite;
2) allowing glutamic acid fermentation wastewater to enter a sedimentation tank, naturally settling, performing solid-liquid separation to obtain sediment and supernatant, discharging the supernatant into a treatment tank, adjusting the pH to 6.5, adding 0.09% of modified montmorillonite for treatment for 24h, filtering, collecting waste modified montmorillonite, and discharging liquid for agricultural irrigation or boiler cooling;
3) adding the waste modified montmorillonite, the waste mycoprotein and the fermentation wastewater into a stirring tank according to the proportion of 5kg to 2kg to 8L, stirring at 500rpm for 15min, then entering a reaction tank, controlling the temperature of the reaction tank to be 100 ℃, reacting for 30min, and then cooling to room temperature to obtain a mixed feed liquid; uniformly mixing the mixed feed liquid, monoammonium phosphate and urea according to the mass ratio of 5:2:1, adding the mixture into a double-screw granulator for granulation, and drying to obtain the fertilizer.
Example 3
The treatment effect of the adsorbent type on the wastewater.
The main indexes of the glutamic acid fermentation wastewater entering the treatment tank are as follows: COD is 3562mg/L, ammonia nitrogen is 361mg/L, SS is 287mg/L, pH4.8; the treatment time of the adsorbent is 36h, the effluent index is monitored, the conventional activated carbon and montmorillonite are used as a reference, the modified montmorillonite prepared in example 1 is used as a research object, and the removal rate of each main pollutant is calculated, as shown in figure 1, compared with the conventional activated carbon and montmorillonite adsorbent, the modified montmorillonite is subjected to acid activation treatment, the interlayer distance is increased due to the action of acid, the interlayer distance is increased by more than 1nm compared with that of unmodified montmorillonite, and the nano activated carbon is deposited on the surface of the montmorillonite through complexation, and as the nano activated carbon has a large specific surface area and various active groups on the surface, the nano activated carbon can be matched with the montmorillonite to fully adsorb the pollutants, and can enrich microorganisms in the wastewater to be used as an attachment carrier of the microorganisms; the effects of unmodified montmorillonite and a conventional activated carbon adsorbent are not ideal, the spacing between layers of the unmodified montmorillonite is relatively small, and a water film is contained, so that the adsorption of pollutants is not facilitated; and the activated carbon is in a saturated adsorption state too early, and the adsorption capacity to pollutants is relatively poor.
Example 4
The effect of different acids on the modification of montmorillonite.
Sulfuric acid and acetic acid are selected as reference, ammonia nitrogen is used as pollutant index to detect the influence of modified montmorillonite types prepared by different acids on the removal rate, the concentration of each group of acid is respectively set to be 1,5,10,15 and 20 percent (shown in figure 2), and compared with sulfuric acid and acetic acid, the removal rate of pollutants is higher when montmorillonite is treated by citric acid acidification; when the montmorillonite is acidized by strong acid, certain damage is generated to the composition structure of the montmorillonite, and when acetic acid with relatively weak acidity is adopted, cations cannot be effectively replaced; the acidity of the citric acid is moderate, and the active groups on the montmorillonite cannot be greatly influenced.
2. Influence of different nano activated carbon addition amounts on montmorillonite modification.
The mass parts of the nano activated carbon powder in the montmorillonite powder are respectively 0,10,20,30,40 and 50 percent, as shown in figure 3, the removal rate of ammonia nitrogen is increased along with the increase of the addition amount of the nano activated carbon, when the addition amount is increased to 30 percent, the removal rate of ammonia nitrogen reaches a peak value, the amount of the activated carbon is continuously increased, the adsorption effect is not obviously affected, probably because the excessive addition amount of the activated carbon exceeds the load capacity of the surface of the montmorillonite, and the addition amount of 30 percent is more suitable.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (4)
1. A method for secondary value-added utilization of amino acid fermentation wastewater comprises the following steps:
step 1) preparation of modified montmorillonite: crushing montmorillonite powder, sieving with a 50-mesh sieve, collecting undersize, drying and dehydrating at 100 deg.C for 30-60min, taking out montmorillonite powder, and mixing with 1 g: adding 1-3ml of citric acid aqueous solution, performing soaking modification treatment at 60 deg.C for 60min under heat preservation condition, adding nanometer activated carbon, increasing reaction temperature to 70 deg.C, centrifuging at 500rpm for 3-5min under heat preservation condition for 60min, collecting precipitate, and oven drying at low temperature to obtain modified montmorillonite;
the mass fraction of the citric acid aqueous solution is 5-15%;
the addition amount of the nano activated carbon is 20-40% by mass of montmorillonite powder;
step 2) fermentation wastewater treatment: allowing glutamic acid fermentation wastewater to enter a sedimentation tank, naturally settling, performing solid-liquid separation to obtain sediment and supernatant, discharging the supernatant into a treatment tank, adjusting the pH to 6-7, adding modified montmorillonite for treatment, filtering, collecting waste modified montmorillonite, and discharging liquid for field irrigation or boiler cooling;
the addition amount of the modified montmorillonite accounts for 0.05-0.1% of the weight of the wastewater, and the treatment time is 24-48 h;
step 3) preparing a fertilizer: adding the waste modified montmorillonite, the glutamic acid fermentation waste mycoprotein and the glutamic acid fermentation waste water into a stirring tank according to the proportion of 3-5kg:1-2kg:5-8L, stirring at 500rpm for 15-30min, then feeding into a reaction tank, controlling the temperature of the reaction tank at 100 ℃, reacting for 30-60min, and then cooling to room temperature to obtain a mixed liquid; uniformly mixing the mixed feed liquid, monoammonium phosphate and urea according to the mass ratio of 3-5:1-2:1-2, adding the mixture into a double-screw granulator for granulation, and drying to obtain the fertilizer.
2. The method according to claim 1, wherein the mass fraction of the aqueous citric acid solution is 10%.
3. The method according to claim 1, wherein the nano activated carbon is added in an amount of 30% by mass of the montmorillonite powder.
4. The method according to any one of claims 1 to 3, wherein the spent mycoprotein of glutamic acid fermentation and the waste water of glutamic acid fermentation are obtained by the following steps:
preparing glutamic acid fermentation liquor by utilizing corynebacterium glutamicum fermentation, centrifuging the fermentation liquor, collecting waste mycoprotein and filtrate of glutamic acid fermentation, extracting the filtrate to prepare glutamic acid, and using glutamic acid fermentation wastewater produced in the extraction process for later use.
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| CN104230444A (en) * | 2014-10-08 | 2014-12-24 | 内蒙古阜丰生物科技有限公司 | Method for preparing fertilizers with sodium glutamate production waste |
| CN104262014A (en) * | 2014-10-07 | 2015-01-07 | 内蒙古阜丰生物科技有限公司 | Biological bacterial fertilizer prepared from glutamic acid fermentation wastes |
| CN109232084A (en) * | 2018-10-18 | 2019-01-18 | 山东福瑞达生物科技有限公司 | A method of polyglutamic acid fertilizer synergist is produced using discarded diatomite |
| CN110496596A (en) * | 2018-05-18 | 2019-11-26 | 南京理工大学 | Charcoal-montmorillonite composite material and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104262014A (en) * | 2014-10-07 | 2015-01-07 | 内蒙古阜丰生物科技有限公司 | Biological bacterial fertilizer prepared from glutamic acid fermentation wastes |
| CN104230444A (en) * | 2014-10-08 | 2014-12-24 | 内蒙古阜丰生物科技有限公司 | Method for preparing fertilizers with sodium glutamate production waste |
| CN110496596A (en) * | 2018-05-18 | 2019-11-26 | 南京理工大学 | Charcoal-montmorillonite composite material and its preparation method and application |
| CN109232084A (en) * | 2018-10-18 | 2019-01-18 | 山东福瑞达生物科技有限公司 | A method of polyglutamic acid fertilizer synergist is produced using discarded diatomite |
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