CN112607968A - Adsorbent for wastewater treatment and preparation method thereof - Google Patents

Adsorbent for wastewater treatment and preparation method thereof Download PDF

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Publication number
CN112607968A
CN112607968A CN202011503725.4A CN202011503725A CN112607968A CN 112607968 A CN112607968 A CN 112607968A CN 202011503725 A CN202011503725 A CN 202011503725A CN 112607968 A CN112607968 A CN 112607968A
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treatment
wastewater
adsorbent
mordenite
flocculation
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毛强平
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Nanjing Xiaoxiang Engineering Technology Co ltd
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Nanjing Xiaoxiang Engineering Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
    • C02F1/048—Purification of waste water by evaporation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5281—Installations for water purification using chemical agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F2001/007—Processes including a sedimentation step
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
    • C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/06—Controlling or monitoring parameters in water treatment pH
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/30—Aerobic and anaerobic processes

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  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Water Treatment By Electricity Or Magnetism (AREA)

Abstract

The invention relates to an adsorbent for wastewater treatment and a preparation method thereof, belonging to the field of wastewater treatment. The method comprises the following steps: soaking mordenite in hydrochloric acid for activation, filtering out and washing a solid after activation treatment, and then roasting to obtain acid-activated mordenite; adding 5-8 parts by weight of acid-activated mordenite and 2-4 parts by weight of dodecyl trimethyl ammonium bromide into 80-100 parts by weight of 50-65 vol.% ethanol water solution, treating at 20-30 ℃, filtering out a product, and drying to obtain surface cation modified mordenite; preparing a dimethylacetamide mixed solution containing 12-18 wt% of polyethersulfone and 10-12 wt% of surface cation modified mordenite, uniformly stirring, dropwise adding the mixed solution into deionized water to form microspheres, carrying out centrifugal treatment, separating the microspheres, and carrying out vacuum drying.

Description

Adsorbent for wastewater treatment and preparation method thereof
Technical Field
The invention relates to an adsorbent for wastewater treatment and a preparation method thereof, belonging to the field of wastewater treatment.
Background
Vitamin B2 (chemical formula: C)17H20N4O6) Riboflavin, also known as riboflavin, is sparingly soluble in water and is stable when heated in neutral or acidic solutions. In organisms, the riboflavin exists in the form of flavin mononucleotide and flavin adenine dinucleotide, directly participates in the biological oxidation of carbohydrates, proteins and fats, and has various physiological functions in organisms, so that the riboflavin has wide application prospects in the aspects of food, feed, medical industry and the like. Because the chemical synthesis method is complex and high in cost, the riboflavin is mainly produced by a microbial fermentation method.
At present, there are mainly 4 kinds of riboflavin production processes: the method comprises a plant extraction method, a chemical synthesis method, a microbial fermentation method and a semi-microbial fermentation synthesis method, wherein the microbial fermentation method is an economic and effective method developed in recent years, and the method for producing the riboflavin has the advantages of low cost, short production period, high product purity and the like, and is a development trend of industrially producing the riboflavin at home and abroad. The method for extracting riboflavin from fermentation liquor mainly comprises a heavy metal salt precipitation method, a Morehouse method, an acid dissolution method and an alkali dissolution method, and the acid dissolution method is mostly adopted in industrial production. The energy consumption for extracting the riboflavin by the acid dissolution method is large, the purity of the riboflavin obtained by one-time dissolution and crystallization is only 60-70%, so that the wastewater generated by the fermentation method is mainly strong-acid wastewater from which the vitamin B2 is extracted. The existing wastewater treatment process mainly removes salt and thallus residues in wastewater by multi-effect evaporation, the distilled wastewater is subjected to biochemical treatment, the original treatment of the evaporated residues is landfill, but the evaporated residues cannot be treated along with the emergence of an increasingly strict environmental protection method, so that the development of a new wastewater treatment process is particularly important. CN202881044U designs and develops a set of vitamin B2 production wastewater treatment system, which comprises a water distribution adjusting tank, an HAF anaerobic reaction tank, an FSBBR flow-away biological reaction tank, an ozone oxidation tank, a TBF secondary biochemical treatment tank, a sedimentation tank and a water outlet, wherein the system mainly adopts a biochemical method to treat wastewater to reach the standard and discharge, but does not recover vitamin B2 in the wastewater. CN106477795A also adopts a membrane treatment technology, adopts a combined system of a ceramic microfiltration membrane, a ceramic nanofiltration membrane and an organic nanofiltration membrane to treat vitamin B2 wastewater and recover vitamin B2, salt and water in the wastewater, but the patent mainly treats strong acid wastewater in the vitamin B2 wastewater and does not relate to wastewater treatment of vitamin B2 fermentation liquor.
Disclosure of Invention
The invention solves the treatment problem of vitamin B2 production wastewater and strong acid wastewater through a series of processes such as flocculation precipitation, a centrifugal machine, a membrane separation technology, a multi-effect evaporation system and the like, and simultaneously recovers vitamin B2 products and proteins in the wastewater.
A method for treating fermentation liquor wastewater comprises the following steps:
step 1, performing first flocculation treatment on fermentation liquor wastewater, and separating sludge;
step 2, performing second flocculation treatment on the clear liquid after the first flocculation treatment, and separating sludge;
step 3, concentrating the clear liquid subjected to the second flocculation treatment by using a nanofiltration membrane, and concentrating and drying the nanofiltration concentrated liquid to obtain vitamin B2;
the fermentation liquor wastewater is vitamin B2 production wastewater and/or strong acid wastewater.
In one embodiment, the sludge obtained by flocculation in the step 1 and/or the step 2 is dried and reused as recycled feed.
In one embodiment, the supernatant of the nanofiltration membrane is sent to a biochemical process.
In one embodiment, the concentration in step 3 is performed by using a triple effect evaporator.
In one embodiment, the pH condition of the first flocculation treatment is 3 to 6; the pH condition of the second flocculation treatment is 8-10.
In one embodiment, the rejection rate of the nanofiltration membrane to 2g/L magnesium sulfate is 96-99% under 0.7 MPa; the cut-off molecular weight of the nanofiltration membrane is 200-500 Da.
In one embodiment, the drying process is spray drying.
In one embodiment, the biochemical treatment comprises anaerobic treatment and aerobic treatment.
In one embodiment, the step 1 and/or the step 2 is performed by centrifugal separation.
A fermentation liquor wastewater treatment device comprises:
the neutralizing tank is used for carrying out a neutralization reaction on the fermented acidic wastewater;
the NaOH adding tank is connected with the neutralizing tank and is used for adding NaOH into the neutralizing tank;
the electrodialyzer is connected with the neutralization tank and is used for performing electrodialytic desalination on the wastewater after the neutralization reaction;
a divalent salt adding tank connected to the dilute liquid side of the electrodialyzer and used for adding divalent salt into the desalted wastewater;
the first flocculation tank is connected to the dilute liquid side of the electrodialyzer and is used for flocculating the electrodialyzer dilute liquid;
the first solid-liquid separation device is connected with the first flocculation tank and is used for performing solid-liquid separation treatment on the feed liquid subjected to flocculation treatment in the first flocculation tank;
the second flocculation tank is connected with the first solid-liquid separation device and is used for flocculating the clear liquid obtained by the first solid-liquid separation device;
the second solid-liquid separation device is connected with the second flocculation tank and is used for performing solid-liquid separation treatment on the feed liquid subjected to flocculation treatment in the second flocculation tank;
the first dryer is connected with the first solid-liquid separation device and/or the second solid-liquid separation device and is used for drying the solid obtained by solid-liquid separation;
the nanofiltration membrane is connected to the second solid-liquid separation device and is used for concentrating and filtering the clear liquid obtained by the second solid-liquid separation device;
the precipitation reaction tank is connected to the concentrated solution side of the nanofiltration membrane and is used for carrying out precipitation separation on divalent salt on the nanofiltration concentrated solution;
the precipitator adding tank is connected with the precipitation reaction tank and is used for adding a precipitator of divalent salt into the precipitation reaction tank;
the microfiltration membrane is connected with the precipitation reaction tank and used for filtering the generated divalent salt precipitate;
and the second dryer is connected with the microfiltration membrane and is used for drying the filtrate obtained from the microfiltration membrane.
Further comprising:
and the first flocculating agent adding tank is used for adding a flocculating agent into the first flocculating tank.
And the second flocculating agent adding tank is used for adding a flocculating agent into the second flocculating tank.
And the first pH regulator is added into the tank and used for regulating the pH value of the material in the first flocculation tank.
And the second pH regulator adding tank is used for adding a flocculating agent into the first flocculating tank.
And the biochemical treatment system is connected with the nanofiltration membrane and is used for performing biochemical treatment on the clear liquid obtained by the nanofiltration membrane.
In one embodiment, the first solid liquid separation device and/or the second solid liquid separation device is a centrifuge.
In one embodiment, the biochemical system comprises one or a combination of two of an anaerobic reaction unit and/or an aerobic reaction unit.
In one embodiment, the first dryer is an oven.
In one embodiment, the second dryer is a spray dryer.
Advantageous effects
In the process, the combination of flocculation precipitation, centrifugal separation, membrane separation and other technologies is adopted to recover the protein and the vitamin B2 in the production wastewater, compared with the multi-effect evaporation of the original treatment process, the process does not produce solid waste, has lower operating cost, and simultaneously recovers the protein and the vitamin B2 in the wastewater, thereby realizing the comprehensive utilization of resources.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a diagram of the apparatus employed;
wherein, 1, a neutralization tank; 2. adding NaOH into a tank; 3. an electrodialyzer; 4. a divalent salt feeding tank; 5. a first flocculation tank; 6. a second flocculation tank; 7. a first flocculating agent is added into the tank; 8. a first pH regulator is added into the tank; 9. a second flocculating agent is added into the tank; 10. adding a second pH regulator into the tank; 11. a first solid-liquid separation device; 12. a second solid-liquid separation device; 13. a first dryer; 14. a nanofiltration membrane; 15. a biochemical treatment system; 16. a precipitation reaction tank; 17. a precipitant addition tank; 18. a microfiltration membrane; 19. a second dryer.
Detailed Description
The term "removal" in the present specification includes not only a case where a target substance is completely removed but also a case where the target substance is partially removed (the amount of the substance is reduced). "purification" in this specification includes the removal of any or specific impurities.
The words "include," "have," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to those elements, but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
The percentages recited in the present invention refer to mass percentages unless otherwise specified.
The invention provides a method and a device for treating fermentation liquor wastewater, which are mainly applied to a comprehensive treatment process for recycling vitamin B2 production wastewater, and comprise the following steps:
step 1, neutralizing acidic wastewater obtained in the fermentation production process of vitamin B2 by using NaOH;
step 2, desalting the neutralized fermentation liquor wastewater in the step 1 by adopting an electrodialysis method;
step 3, adding divalent salt ions into the desalted water obtained in the step 2;
step 4, performing first flocculation treatment on the neutralized fermentation liquor wastewater obtained in the step 3, and separating sludge;
step 5, performing second flocculation treatment on the clear liquid subjected to the first flocculation treatment in the step 4, and separating sludge;
step 6, concentrating the clear liquid subjected to the second flocculation treatment by adopting a nanofiltration membrane;
and 7, adding a precipitator into the nanofiltration concentrated solution to precipitate divalent salt ions, filtering the solution by using a microfiltration membrane to remove the precipitate, and concentrating and drying the filtrate of the microfiltration membrane to obtain the vitamin B2.
In the step 1, NaOH is adopted to neutralize the acidic wastewater so as to make the pH value neutral, so that an electrodialysis membrane in a subsequent electrodialysis unit can be protected; in the step 2, the electrodialysis method is not influenced by the composition of raw materials, inorganic salts in the feed liquid can be partially removed effectively, a certain amount of inorganic salts are contained in the acidic wastewater of the fermentation liquor, and in the process of NaOH neutralization, more inorganic salts such as NaCl and the like can be obtained due to neutralization reaction, the step has two functions, the content of NaCl can be effectively reduced in the electrodialysis treatment process, the influence of the inorganic salts on the formation of colloid double-electrode layers in the flocculation process can be reduced, the flocculation effect can be improved, the subsequent operation load of a nanofiltration membrane can be reduced, and the current density of the electrodialysis is 40A/m2～500A/m2(ii) a Secondly, in the step 6, a nanofiltration membrane is required to be used for concentrating and separating the vitamin B2, and the existence of inorganic salt can cause the membrane pores of the nanofiltration membrane to have a tendency of expanding and reduce the retention rate of organic matters, so that the retention rate of the nanofiltration membrane on the vitamin B2 can be improved and the recovery yield can be improved after the inorganic salt is removed by adopting an electrodialysis mode; in step 3, a divalent salt (e.g., Ca) is added2+、Zn2+、Mg2+Etc.), which mainly produce two effects, one is that, because the divalent salt can effectively denature the protein and reduce the solubility of the protein, the flocculation effect can be improved, the COD of the flocculated clear solution can be reduced, and the recovery amount of the protein can be improved; when the flocculation process is completed, the flocculated clear liquid is subjected to nanofiltration separation, the nanofiltration membrane has higher retention rate for divalent salt, when the divalent salt is retained on the concentration side of the membrane, due to the charge balance Donnan effect in the nanofiltration process, more NaCl is forced to permeate the nanofiltration membrane, even the phenomenon of 'monovalent salt negative retention' occurs, so as to maintain the charge balance of the two membranes, after the NaCl permeates, the purity of vitamin B2 in the trapped liquid can be better, and since the divalent salt is easier to remove by a precipitation method than the monovalent salt, the subsequent method can adopt, for example, OH-The addition of the precipitant removes the divalent salt, and the technical idea of the step is to utilizeThe two salt ions exchange, so that the recovery purity is improved, and the salt is easier to remove. In the step 4, in the primary flocculation precipitation process, a flocculating agent is added to perform flocculation precipitation under the condition that the pH = 3-6, so that thalli and macromolecular proteins in the production wastewater are polymerized, flocculated and precipitated, and then the thalli and the macromolecular proteins are centrifugally separated by a centrifugal machine. The natural flocculating agent can be used for flocculation under the acidic condition, such as lignin flocculating agent, and the natural flocculating agent has the advantages of good biodegradability, no toxicity and the like, so that the feed obtained by applying the natural flocculating agent to protein flocculation is more suitable for animals; in the step 5, a flocculating agent is added to perform secondary flocculation precipitation under the condition that the pH = 8-10 in the secondary flocculation precipitation process, so that the main purpose is to flocculate and precipitate the soluble small molecular protein, and then a centrifugal machine is used for centrifugal separation. In the step, polyaluminium chloride can be used as a flocculating agent, and most of protein is removed by using a natural flocculating agent in the first step, so that only a small amount of chemical flocculating agent is needed in the protein flocculation process, the quality of the recovered protein feed is further improved, and a synergistic effect is generated by the front-back matching of the first flocculating agent and the second flocculating agent, so that the problems of protein recovery and quality are solved; the sludge after twice centrifugation is made into protein feed by drying equipment such as cyclone drying equipment and the like; in the step 6, the nanofiltration process is that the centrifuged clear liquid enters a nanofiltration membrane system, vitamin B2 is separated out through the nanofiltration membrane, and the rejection rate of the nanofiltration membrane to 2g/L magnesium sulfate is 96-99% under 0.7 MPa; the interception and separation capacity of the nanofiltration membrane is preferably 200-500 Da; after the nanofiltration concentrate is obtained, NaOH can be added to precipitate divalent salts, and the precipitate is removed by using a microfiltration membrane; concentrating the filtrate with multi-effect evaporator, and spray drying to obtain vitamin B2The product of (2) is subjected to a biochemical system treatment by nanofiltration clear liquid, wherein the biochemical system comprises an anaerobic tank and an aerobic tank.
Based on the above method, the present invention further provides a processing apparatus, as shown in fig. 2, including:
the neutralizing tank 1 is used for carrying out a neutralizing reaction on the fermented acidic wastewater;
the NaOH adding tank 2 is connected to the neutralizing tank 2 and is used for adding NaOH into the neutralizing tank 1;
the electrodialyzer 3 is connected with the neutralization tank 1 and is used for performing electrodialytic desalination on the wastewater after neutralization reaction;
a divalent salt adding tank 4 connected to the dilute liquid side of the electrodialyzer 3 for adding divalent salt to the desalted wastewater;
a first flocculation tank 5 connected to the dilute solution side of the electrodialyzer 4 for performing flocculation treatment on the electrodialyzed dilute solution;
the first solid-liquid separation device 11 is connected to the first flocculation tank 5 and is used for performing solid-liquid separation treatment on the feed liquid subjected to flocculation treatment in the first flocculation tank 5;
the second flocculation tank 6 is connected to the first solid-liquid separation device 11 and is used for flocculating the clear liquid obtained by the first solid-liquid separation device 11;
the second solid-liquid separation device 12 is connected to the second flocculation tank 6 and is used for performing solid-liquid separation treatment on the feed liquid flocculated in the second flocculation tank 6;
a first dryer 13 connected to the first solid-liquid separator 11 and/or the second solid-liquid separator 12, for drying the solid obtained by the solid-liquid separation;
a nanofiltration membrane 14 connected to the second solid-liquid separation device 12 and used for concentrating and filtering the clear liquid obtained by the second solid-liquid separation device 12;
a precipitation reaction tank 16 connected to the concentrated solution side of the nanofiltration membrane 14 and used for performing precipitation separation of divalent salt on the nanofiltration concentrated solution;
a precipitant adding tank 17 connected to the precipitation reaction tank 16 for adding a precipitant of divalent salt into the precipitation reaction tank 16;
a microfiltration membrane 18 connected to the precipitation reaction tank 16 for filtering the generated divalent salt precipitate;
and a second dryer 19 connected to the microfiltration membrane 18 for drying the filtrate obtained from the microfiltration membrane 18.
Further comprising:
a first flocculating agent addition tank 7 for adding a flocculating agent to the first flocculating tank 5.
And a second flocculating agent adding tank 9 for adding a flocculating agent into the second flocculating tank 6.
The first pH regulator is added into the tank 8 and is used for regulating the pH value of the material in the first flocculation tank 5.
A second pH adjuster addition tank 9 for adding a flocculant to the first flocculation tank 6.
And the biochemical treatment system 15 is connected to the nanofiltration membrane 14 and is used for performing biochemical treatment on the clear liquid obtained by the nanofiltration membrane 14.
In one embodiment, the first solid liquid separation device 11 and or the second solid liquid separation device 12 is a centrifuge.
In one embodiment, the biochemical system 15 includes one or a combination of an anaerobic reaction unit and/or an aerobic reaction unit.
In one embodiment, the first dryer 13 is an oven.
In one embodiment, the second dryer 19 is a spray dryer.
The vitamin B2 process wastewater treated in the following examples was from the production of strongly acidic wastewater with the water quality as shown in the following table:
VB2 mg/L COD mg/L BOD5 mg/L SS mg/L pH NaCl g/L
quality of water 1680 61375 48000 51250 2～3 8.4
In the following examples, protein content was determined by the biuret method; the retention rate of the inorganic salt is measured by an ICP method; the content of vitamin B2 is detected by fluorescence spectrophotometry.
Example 1
Adding NaOH to adjust the pH value of the strongly acidic wastewater from the fermentation process of vitamin B2 to 6.5-7, and then adjusting the pH value to 80A/m2Performing electrodialysis desalination treatment under current density condition to remove Na+The concentration is reduced by about 35 percent, CaCl is added into the electrodialyzed weak solution2Is prepared by reacting CaCl2Is 1 wt%; performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating with a lignin flocculant, wherein the addition amount is 250ppm, adjusting the pH to 8-9, then performing secondary flocculation centrifugal separation, and performing flocculation with polyaluminium chloride, wherein the addition amount is 70 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 200Da, the operating pressure is 3.0MPa, and the concentration multiple of the concentration membrane is about 5 times.
Adding NaOH into the nanofiltration concentrated solution to lead CaCl to be2Precipitating with microfiltration membrane with pore diameter of 50nm, removing precipitate, evaporating the microfiltration filtrate, and spray drying to obtain vitamin B2The product of (1).
Example 2
Adding NaOH to adjust the pH value of the strongly acidic wastewater from the fermentation process of vitamin B2 to 6.5-7, and then adjusting the pH value to 120A/m2Performing electrodialysis desalination treatment under current density condition to remove Na+The concentration is reduced by about 30 percent, CaCl is added into the electrodialyzed weak solution2Is prepared by reacting CaCl2Is 1.2 wt%; performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating by using a lignin flocculant, wherein the addition amount is 350ppm, adjusting the pH to 8-9, then performing secondary flocculation centrifugal separation, and performing flocculation by using polyaluminium chloride, wherein the addition amount is 50 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 400Da, the operating pressure is 3.5MPa, and the concentration multiple of the concentration membrane is about 5 times.
Adding NaOH into the nanofiltration concentrated solution to lead CaCl to be2Precipitating with microfiltration membrane with pore diameter of 50nm, removing precipitate, evaporating the microfiltration filtrate, and spray drying to obtain vitamin B2The product of (1).
Example 3
Adding NaOH to regulate the pH value of the strongly acidic wastewater from the fermentation process of vitamin B2 to 6.5-7, and then regulating the pH value at 140A/m2Performing electrodialysis desalination treatment under current density condition to remove Na+The concentration is reduced by about 35 percent, CaCl is added into the electrodialyzed weak solution2Is prepared by reacting CaCl2Is 0.8 wt%; performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating with a lignin flocculant with the addition of 220ppm, adjusting the pH to 8-9, performing secondary flocculation centrifugal separation, and performing flocculation with polyaluminium chloride with the addition of 80 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 500Da, the operating pressure is 3.2MPa, and the concentration multiple of the concentration membrane is about 5 times.
Adding NaOH into the nanofiltration concentrated solution to lead CaCl to be2Precipitating with microfiltration membrane with pore diameter of 50nm, removing precipitate, evaporating the microfiltration filtrate, and spray drying to obtain vitamin B2The product of (1).
Example 4
Adding NaOH to adjust the pH value of the strongly acidic wastewater from the fermentation process of vitamin B2 to 6.5-7, and then adjusting the pH value to 150A/m2Electrodialysis desalination treatment under current density conditionTo make Na+The concentration is reduced by about 40 percent, CaCl is added into the electrodialyzed weak solution2Is prepared by reacting CaCl2Is 1.3 wt%; performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating by using a lignin flocculant, wherein the addition amount is 280ppm, adjusting the pH to 8-9, then performing secondary flocculation centrifugal separation, and performing flocculation by using polyaluminium chloride, wherein the addition amount is 65 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 400Da, the operating pressure is 2.5MPa, and the concentration multiple of the concentration membrane is about 4 times.
Adding NaOH into the nanofiltration concentrated solution to lead CaCl to be2Precipitating with microfiltration membrane with pore diameter of 50nm, removing precipitate, evaporating the microfiltration filtrate, and spray drying to obtain vitamin B2The product of (1).
Comparative example 1
The differences from example 1 are: the wastewater is not subjected to electrodialysis desalination treatment.
Adding NaOH to adjust the pH value of the strongly acidic wastewater from the fermentation process of vitamin B2 to 6.5-7, and then adding CaCl2Is prepared by reacting CaCl2Is 1 wt%; performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating with a lignin flocculant, wherein the addition amount is 250ppm, adjusting the pH to 8-9, then performing secondary flocculation centrifugal separation, and performing flocculation with polyaluminium chloride, wherein the addition amount is 70 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 200Da, the operating pressure is 3.0MPa, and the concentration multiple of the concentration membrane is about 5 times.
Adding NaOH into the nanofiltration concentrated solution to lead CaCl to be2Precipitating with microfiltration membrane with pore diameter of 50nm, removing precipitate, evaporating the microfiltration filtrate, and spray drying to obtain vitamin B2The product of (1).
Comparative example 2
The differences from example 1 are: adding CaCl into the dilute solution without electrodialysis2。
Adding NaOH to regulate the strong acid wastewater from the fermentation process of vitamin B2The pH value is 6.5-7 and then is 80A/m2Performing electrodialysis desalination treatment under current density condition to remove Na+Reducing the concentration by about 35%, performing primary flocculation centrifugal separation again, adjusting the pH to 4-5, then treating by using a lignin flocculant, wherein the addition amount is 250ppm, adjusting the pH to 8-9, performing secondary flocculation centrifugal separation, and performing flocculation by using polyaluminium chloride, wherein the addition amount is 70 ppm; and (5) drying the twice flocculated sludge to obtain the protein feed.
And (3) allowing the clear liquid of the secondary centrifuge to enter a nanofiltration membrane system, wherein the molecular weight cut-off of the nanofiltration membrane is 200Da, the operating pressure is 3.0MPa, and the concentration multiple of the concentration membrane is about 5 times.
Filtering the nanofiltration concentrated solution with a microfiltration membrane with the aperture of 50nm, evaporating and spray-drying the microfiltration filtrate to obtain the vitamin B-containing solution2The product of (1).
The operation procedures and the detection results of the recovered products of the above examples and comparative examples are as follows:
Figure DEST_PATH_IMAGE002
as can be seen from the above table, the method of the present invention can recover crude protein from fermentation wastewater, and can directly apply the crude protein to animal feed, and simultaneously, can recover crude vitamin B2 in the fermentation wastewater, and can further purify the crude vitamin B2 for use in animal feed additives. As can be seen from the example 1 and the comparative example 1, in the example 1, after the electrodialysis desalination is performed on the acidic wastewater, NaCl in the wastewater subjected to flocculation can be reduced, so that the retention rate of the vitamin B2 on the nanofiltration membrane is obviously improved, and the recovery rate of the vitamin B2 is improved, so that after the concentration of NaCl is reduced, the effect of a double electric layer of a flocculant in the flocculation process is weakened, and the effect of removing COD by flocculation is better; as can be seen from the example 1 and the comparative example 2, the rejection of monovalent salt NaCl is improved through the Donnan effect of the nanofiltration membrane by adding divalent salt ions into the electrodialysis dilute solution, so that the rejection rate of the nanofiltration membrane on NaCl is reduced, and meanwhile, the purity and the recovery rate of the flocculated protein are improved because the solubility of the protein and the polypeptide is reduced by the divalent salt.

Claims (7)

1. The adsorbent for treating waste water features that it is polyether sulfone modified mordenite microsphere.
2. The method for preparing an adsorbent for wastewater treatment according to claim 1, comprising the steps of:
step a, soaking mordenite in hydrochloric acid for activation, filtering out and washing a solid after activation treatment, and then performing roasting treatment to obtain acid-activated mordenite;
step b, adding 5-8 parts by weight of acid-activated mordenite and 2-4 parts by weight of dodecyl trimethyl ammonium bromide into 80-100 parts by weight of 50-65 vol.% ethanol water solution, treating at 20-30 ℃, filtering out a product, and drying to obtain surface cation modified mordenite;
and c, preparing a dimethylacetamide mixed solution containing 12-18 wt% of polyether sulfone and 10-12 wt% of surface cation modified mordenite, uniformly stirring, dropwise adding the mixed solution into deionized water to form microspheres, performing centrifugal treatment, separating the microspheres, and performing vacuum drying to obtain the polyether sulfone modified mordenite microsphere adsorbent.
3. The method for preparing the adsorbent for wastewater treatment according to claim 2, wherein in the step a, the roasting treatment parameter is 160-170 ℃ for 0.5-1 h.
4. The method for preparing the adsorbent for wastewater treatment according to claim 2, wherein the concentration of hydrochloric acid in step a is 1-5 mol/L.
5. The method for preparing an adsorbent for wastewater treatment according to claim 2, wherein the activation time in step a is 30-50 min.
6. The method for preparing the adsorbent for wastewater treatment according to claim 2, wherein in the step b, the treatment time is 5-8 h.
7. Use of the adsorbent for wastewater treatment according to claim 1 for treatment of fermentation wastewater.
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