CN111559824A - Method and device for recycling protein wastewater - Google Patents
Method and device for recycling protein wastewater Download PDFInfo
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- CN111559824A CN111559824A CN201911299980.9A CN201911299980A CN111559824A CN 111559824 A CN111559824 A CN 111559824A CN 201911299980 A CN201911299980 A CN 201911299980A CN 111559824 A CN111559824 A CN 111559824A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F9/00—Multistage treatment of water, waste water or sewage
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- 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
- C02F1/10—Treatment of water, waste water, or sewage by heating by distillation or evaporation by direct contact with a particulate solid or with a fluid, as a heat transfer medium
- C02F1/12—Spray evaporation
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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Abstract
The invention provides a method for recovering sericin from sericin wastewater. The method comprises the following steps: (1) clarifying the sericin wastewater by a microfiltration membrane; (2) continuously carrying out ultrafiltration membrane classification on the penetrating fluid obtained in the step (1); (3) after grading is finished, concentrating the penetrating fluid in the step (2) by using an ultrafiltration membrane; (4) and (4) drying the concentrated solution in the step (3) to obtain sericin. The method disclosed by the invention is simple, high in desalination rate, safe and environment-friendly, and high in sericin recovery rate, and can be used for recycling the available protein in a grading manner without adding any chemical reagent.
Description
Technical Field
The invention relates to a method and a device for recycling protein wastewater, in particular to a method for efficiently recycling sericin from sericin wastewater, belonging to the field of food and feed.
Background
Sericin is a natural high molecular protein, which accounts for about 20-30% of the total silk protein, and exists in a large amount in reeling, dyeing and scouring, silk weaving, silk spinning and silk cotton processing engineering. At present, the removed sericin is discarded as waste liquid, so that a large amount of biological resources are wasted, and serious water pollution is caused, so that the recovery, development and utilization of the sericin are slow. Because the sericin wastewater has large volume and complex components, the sericin content is low, the recovery is difficult, and the energy consumption is high by direct evaporation.
Disclosure of Invention
The purpose of the invention is: provides a method and a device for recovering sericin from sericin wastewater. The process reduces the discharge of sericin wastewater, and recovers sericin from the wastewater. The method is simple, does not add any chemical reagent, is safe and environment-friendly, and has high sericin recovery rate and high comprehensive utilization rate.
A method for recycling protein wastewater comprises the following steps:
step 1, carrying out microfiltration treatment on the protein wastewater;
step 2, performing first ultrafiltration treatment on the microfiltration permeating liquid, and intercepting macromolecular protein;
step 3, carrying out second ultrafiltration treatment on the permeate of the first ultrafiltration, and concentrating the micromolecular protein;
and 4, sequentially concentrating and spray-drying the permeate of the second ultrafiltration to obtain the recovered micromolecule protein.
In one embodiment, after the surfactant is added into the concentrated solution of the first ultrafiltration for demulsification treatment, cyclone separation is carried out to remove the oil phase, the water phase is subjected to third ultrafiltration treatment to concentrate the macromolecular protein, and the concentrated solution of the third ultrafiltration is sequentially subjected to concentration and spray drying treatment to obtain the water-soluble protein.
In one embodiment, the aqueous phase is treated by a third ultrafiltration after the addition of inorganic salts.
In one embodiment, the surfactant is a cationic surfactant, and the amount of the surfactant can be controlled to be 100-1000 mg/L.
In one embodiment, the inorganic salt is a calcium salt or a magnesium salt, and the amount added may be controlled to be 0.5 to 2 wt%.
In one embodiment, the average pore size of the microfiltration membrane during microfiltration is 0.05 to 1.4 μm.
In one embodiment, the ultrafiltration membrane of the first ultrafiltration process has an average pore size of 4 to 50 nm.
In one embodiment, the ultrafiltration membrane of the second ultrafiltration process has a molecular weight cut-off of 100 to 100000D.
In one embodiment, the ultrafiltration membrane of the third ultrafiltration process has a molecular weight cut-off of 1000 to 300000D.
A recycling device of protein wastewater comprises:
the raw material tank is used for storing sericin wastewater;
the microfiltration membrane is connected with the raw material tank and is used for carrying out microfiltration treatment on the sericin wastewater to remove suspended matter impurities;
the first ultrafiltration membrane is connected to the permeation side of the microfiltration membrane and is used for carrying out ultrafiltration, filtration and purification treatment on the filtrate of the microfiltration membrane to remove macromolecular proteins;
the second ultrafiltration membrane is connected to the permeation side of the first ultrafiltration membrane and used for concentrating the permeation liquid of the first ultrafiltration membrane and intercepting the small-molecule protein;
the concentration device is connected to the interception side of the second ultrafiltration membrane and is used for concentrating the concentrated solution of the second ultrafiltration membrane again;
and the spray drying device is connected with the concentration device and used for carrying out spray drying treatment on the concentrated solution obtained in the concentration device to obtain the micromolecule protein.
In one embodiment, further comprising: the demulsification reaction tank is connected to the interception side of the first ultrafiltration membrane and is used for performing demulsification reaction treatment on the concentrated solution of the first ultrafiltration membrane; the demulsifying reaction tank is also connected with a demulsifying agent feeding tank.
In one embodiment, the demulsifier addition tank is filled with a cationic surfactant.
In one embodiment, further comprising: and the cyclone separator is connected with the demulsification reaction tank and used for performing cyclone separation treatment on the wastewater obtained in the demulsification reaction tank, the oil phase is discharged from the top, and the water phase is discharged from the bottom.
In one embodiment, further comprising: and the third ultrafiltration membrane is connected with the bottom water phase outlet of the cyclone separator and is used for carrying out protein concentration treatment on the water phase in the cyclone separator.
In one embodiment, the retentate side of the third ultrafiltration membrane is connected to a concentration device.
In one embodiment, the liquid inlet of the third ultrafiltration membrane is also connected with an inorganic salt feeding tank.
In one embodiment, the overhead oil phase outlet of the cyclone and/or the permeate side of the third ultrafiltration membrane are connected to a biochemical treatment unit for biochemical treatment of the overhead oil phase and/or the permeate of the third ultrafiltration membrane, respectively.
In one embodiment, the average pore size of the microfiltration membrane is 0.05 to 1.4 μm.
In one embodiment, the first ultrafiltration membrane has an average pore size of 4 to 50 nm.
In one embodiment, the second ultrafiltration membrane has a molecular weight cut-off of 100 to 100000D.
In one embodiment, the third ultrafiltration membrane has a molecular weight cut-off of 1000 to 300000D.
The recycling device of the protein wastewater is applied to recycling the protein in the wastewater.
Advantageous effects
The invention solves the problem of fractional recovery of sericin from sericin wastewater by using a membrane integration technology (ultrafiltration membrane clarification technology and ultrafiltration membrane concentration technology).
The sericin can be obtained by grading and filtering with a microfiltration membrane and concentrating with an ultrafiltration membrane. And evaporating and concentrating the second ultrafiltration membrane concentrated solution to obtain soluble protein, and finally evaporating and crystallizing the ultrafiltration membrane concentrated solution to obtain absorbable protein with the highest value. And no chemical reagent is added in the whole production flow, the operation is safe and environment-friendly, and the sericin recovery rate is high.
Meanwhile, the invention realizes the reutilization of protein for the ultrafiltration concentrated solution obtained in the process of ultrafiltration membrane filtration and purification; the wastewater containing pupa oil and sericin generated in the silk refining process is subjected to demulsification treatment by adding a surfactant, so that emulsified oil drops formed between the pupa oil and the water can be demulsified, and the oil drops after demulsification can be separated by a cyclone separation method; the solubility of the protein is reduced by adding a certain amount of inorganic salt, and the protein can be separated from the surfactant and the inorganic salt by an ultrafiltration method to obtain the protein which is recovered again.
The method realizes the resource utilization of the wastewater and can efficiently obtain products with high recovery value from the wastewater in a grading way. Utilize multichannel membrane to alleviate membrane pollution degree and can effectively get rid of the salinity, compare traditional evaporative concentration, the concentrated energy saving of embrane method reduces cost.
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FIG. 1 is a diagram of the apparatus of the present invention.
Wherein, 1, a raw material tank; 2. a microfiltration membrane; 3. a first ultrafiltration membrane; 4. a second ultrafiltration membrane; 5. a concentration device; 6. a spray drying device; 7. a demulsification reaction tank; 8. a cyclone separator; 9. a third ultrafiltration membrane; 10. an inorganic salt feeding tank; 11. a demulsifier adding tank; 12. a biochemical treatment unit.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments. It will be understood by those skilled in the art that the following examples are illustrative of the present invention only and should not be taken as limiting the scope of the invention. The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Approximating language, as used herein throughout the specification and claims, may be applied to modify any quantitative representation that could permissibly vary without resulting in a change in the basic function to which it is related. Accordingly, a value modified by a term or terms, such as "about," is not to be limited to the precise value specified. In at least some instances, the approximating language may correspond to the precision of an instrument for measuring the value. Unless context or language indicates otherwise, range limitations may be combined and/or interchanged, and such ranges are identified and include all the sub-ranges included herein. Other than in the operating examples, or where otherwise indicated, all numbers or expressions referring to quantities of ingredients, reaction conditions, and so forth used in the specification and claims are to be understood as modified in all instances by the word "about".
The recitation of values by ranges is to be understood in a flexible manner to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range as if each numerical value and sub-range is explicitly recited. For example, a concentration range of "about 0.1% to about 5%" should be interpreted to include not only the explicitly recited concentration of about 0.1% to about 5%, but also include individual concentrations (e.g., 1%, 2%, 3%, and 4%) and sub-ranges (e.g., 0.1% to 0.5%, 1% to 2.2%, 3.3% to 4.4%) within the indicated range.
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 wastewater to be treated in the invention can be selected from the wastewater containing sericin produced in silk reeling, dyeing and scouring, silk weaving, silk spinning and silk cotton processing engineering, and particularly can be the wastewater containing sericin and protein produced in silk processing process, and the water quality COD value of the main wastewater produced in silk spinning cotton making, cocoon cooking, silk reeling, silk refining and other processes is as follows:
| cocoon cooking | Reeling silk | Refining of silk |
| 0.25-0.65 mg/L | 0.117-0.350 mg/L | 17-40 mg/L |
From the above table, it can be seen that COD values of the wastewater generated in the silk processing process are very large, and the COD values are mainly caused by sericin and pupa oil in the wastewater. Therefore, it is necessary to efficiently separate sericin by a suitable process for the recovery.
Taking the treatment of wastewater with high COD value in the silk refining process as an example, the method adopted by the invention is mainly as follows,
firstly, the wastewater is subjected to microfiltration, and the microfiltration aims to remove some solid suspended matters contained in the wastewater and clarify the wastewater.
The wastewater after microfiltration treatment is treated by a first ultrafiltration membrane, wherein the first ultrafiltration membrane is used for removing some macromolecular proteins and some colloidal impurities in the wastewater, especially pupa oil of the wastewater in the silk refining process can form emulsified liquid drops under the high-temperature boiling condition, stable dispersion phases are formed between the liquid drops and the wastewater, and the liquid drops are not easy to separate from water in a natural layering or centrifugal mode, so that the protein is difficult to separate. Therefore, the macromolecular proteins and oily liquid drops can be retained on the concentrated side of the ultrafiltration membrane through the first ultrafiltration membrane, so that the small molecular proteins can permeate the ultrafiltration membrane, the additional value of the small molecular proteins is high, and the small molecular proteins can be recycled through the subsequent process. The aperture of the first ultrafiltration membrane can be controlled within the range of 4-50 nm, so that small molecular proteins can penetrate through the first ultrafiltration membrane effectively, and large molecular proteins and milky oil drops are intercepted.
And concentrating the filtrate obtained by the first ultrafiltration membrane by using a second ultrafiltration membrane, wherein the cut-off molecular weight of the ultrafiltration membrane used is 100-100000D, so that the small molecular proteins can be cut off to obtain a concentrated solution of the ultrafiltration membrane, and the high-value-added small molecular proteins can be recycled. The concentrated solution of the second ultrafiltration membrane can be subjected to further concentration treatment and then spray-dried to obtain the final small-molecule protein.
For the concentrated solution of the first ultrafiltration membrane, which contains macromolecular protein and emulsified oily liquid drops, the invention adds a certain amount of surfactant (such as cationic surfactant, the adding amount can be controlled at 100-1000 mg/L) into the concentrated solution of the first ultrafiltration membrane to carry out demulsification treatment, so that the emulsified liquid drops generated in the high-temperature boiling process can be demulsified, the pupa oil and the wastewater containing protein can be effectively separated through subsequent cyclone separation, and finally the purity after protein recovery can be improved. In the cyclone separation process, the oil phase has low density and is discharged from the top of the cyclone separator, and the water has high density and is discharged from the bottom; the water phase also contains a surfactant, so that a certain amount of inorganic salt (such as calcium salt and magnesium salt, the addition amount can be controlled to be 0.5-2 wt%) is added into the water phase, protein denaturation can be realized, the solubility of the protein is reduced, the molecules of the protein are enlarged, the protein can be more effectively intercepted in the process of concentration by using the third ultrafiltration membrane, and the surfactant can permeate the third ultrafiltration membrane, so that the separation of the protein and the surfactant is facilitated, and the purity of the recovered protein can be finally improved.
Based on the method, the invention also provides a device for recycling the protein wastewater, which comprises the following steps:
the raw material tank 1 is used for storing sericin wastewater;
the microfiltration membrane 2 is connected to the raw material tank 1 and is used for carrying out microfiltration treatment on the sericin wastewater to remove suspended matter impurities;
the first ultrafiltration membrane 3 is connected to the permeation side of the microfiltration membrane 2 and is used for carrying out ultrafiltration, filtration and purification treatment on the filtrate of the microfiltration membrane 2 to remove macromolecular proteins;
the second ultrafiltration membrane 4 is connected to the permeation side of the first ultrafiltration membrane 3 and is used for concentrating the permeation liquid of the first ultrafiltration membrane 3 and intercepting the small-molecule protein;
the concentration device 5 is connected to the interception side of the second ultrafiltration membrane 4 and is used for concentrating the concentrated solution of the second ultrafiltration membrane 4 again;
and the spray drying device 6 is connected to the concentration device 5 and is used for carrying out spray drying treatment on the concentrated solution obtained in the concentration device 5 to obtain the micromolecule protein.
In one embodiment, further comprising: the demulsification reaction tank 7 is connected to the interception side of the first ultrafiltration membrane 3 and is used for performing demulsification reaction treatment on the concentrated solution of the first ultrafiltration membrane 3; the demulsifying reaction tank 7 is also connected with a demulsifying agent adding tank 11.
In one embodiment, the emulsion breaker feed tank 11 contains a cationic surfactant.
In one embodiment, further comprising: and the cyclone separator 8 is connected to the demulsification reaction tank 7 and is used for performing cyclone separation treatment on the wastewater obtained in the demulsification reaction tank 7, discharging the oil phase from the top and discharging the water phase from the bottom.
In one embodiment, further comprising: and the third ultrafiltration membrane 9 is connected to the bottom water phase outlet of the cyclone separator 8 and is used for carrying out protein concentration treatment on the water phase in the cyclone separator 8.
In one embodiment, the retentate side of the third ultrafiltration membrane 9 is connected to the concentration device 5.
In one embodiment, the liquid inlet of the third ultrafiltration membrane 9 is also connected with an inorganic salt feeding tank 2.
In one embodiment, the overhead oil phase outlet of the cyclone separator 8 and/or the permeate side of the third ultrafiltration membrane 9 is connected to a biochemical treatment unit 12, the biochemical treatment unit 12 being adapted to perform biochemical treatment of the overhead oil phase and/or the permeate of the third ultrafiltration membrane 9, respectively.
In one embodiment, the average pore size of the microfiltration membrane 2 is 0.05 to 1.4 μm.
In one embodiment, the first ultrafiltration membrane 3 has an average pore size of 4 to 50 nm.
In one embodiment, the second ultrafiltration membrane 4 has a molecular weight cut-off of 100 to 100000D.
In one embodiment, the third ultrafiltration membrane 9 has a molecular weight cut-off of 1000 to 300000D.
Example 1
(1) Clarifying sericin wastewater in a silk refining process by adopting a hollow fiber membrane with the diameter of 1 mu m, filtering and concentrating;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 20nm ceramic membrane, concentrating by 20 times, and adding washing water with the volume 3 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing filtrate and the penetrating fluid in the step (2) pass through an organic membrane with the molecular weight cutoff of 5000Da, are concentrated to the material concentration of 13 percent, and are added with washing water with the volume of 3 times of that of the concentrated solution for washing and filtering.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
And (3) drying the concentrated solution in the step (2) to obtain soluble protein.
Example 2
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5 mu m ceramic membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 4nm ceramic membrane, concentrating by 25 times, and adding washing water with the volume of 1 time of that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing filtrate and the penetrating fluid in the step (2) pass through an ultrafiltration membrane with the molecular weight cutoff of 50000Da, are concentrated to the material concentration of 15 percent, and are added with washing water with the volume of 1 time of that of the concentrated solution for washing and filtering.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
And (3) drying the concentrated solution in the step (2) to obtain soluble protein.
Example 3
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5-micron organic microfiltration membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 12nm ceramic membrane, concentrating by 23 times, and adding washing water with the volume 2 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing and filtering liquid and penetrating liquid in the step (2) pass through an organic membrane with the molecular weight cutoff of 20000Da, are concentrated to the material concentration of 14 percent, and are added with washing and filtering water with the volume 2 times of that of the concentrated liquid.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
And (3) drying the concentrated solution in the step (2) to obtain soluble protein.
Example 4
(1) Clarifying sericin wastewater in a silk refining process by adopting a hollow fiber membrane with the diameter of 1 mu m, filtering and concentrating;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 20nm ceramic membrane, concentrating by 20 times, and adding washing water with the volume 3 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing filtrate and the penetrating fluid in the step (2) pass through an organic membrane with the molecular weight cutoff of 5000Da, are concentrated to the material concentration of 13 percent, and are added with washing water with the volume of 3 times of that of the concentrated solution for washing and filtering.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) Adding 200mg/L hexadecyl trimethyl ammonium chloride into the concentrated solution in the step (2), heating to 40 ℃, slowly stirring for 30min, performing emulsion breaking treatment, performing cyclone separation treatment, discharging an oil phase from the top, performing biochemical treatment, adding 1% magnesium chloride into a water phase to denature proteins, concentrating by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 100000Da, and drying the concentrated solution to obtain the soluble protein.
Example 5
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5 mu m ceramic membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 4nm ceramic membrane, concentrating by 25 times, and adding washing water with the volume of 1 time of that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing filtrate and the penetrating fluid in the step (2) pass through an ultrafiltration membrane with the molecular weight cutoff of 50000Da, are concentrated to the material concentration of 15 percent, and are added with washing water with the volume of 1 time of that of the concentrated solution for washing and filtering.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) Adding 300mg/L hexadecyl trimethyl ammonium chloride into the concentrated solution in the step (2), heating to 35 ℃, slowly stirring for 40min, performing emulsion breaking treatment, performing cyclone separation treatment, discharging an oil phase from the top, performing biochemical treatment, adding 1% calcium chloride into a water phase to denature proteins, concentrating by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 50000Da, and drying the concentrated solution to obtain the soluble protein.
Example 6
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5-micron organic microfiltration membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 12nm ceramic membrane, concentrating by 23 times, and adding washing water with the volume 2 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing and filtering liquid and penetrating liquid in the step (2) pass through an organic membrane with the molecular weight cutoff of 20000Da, are concentrated to the material concentration of 14 percent, and are added with washing and filtering water with the volume 2 times of that of the concentrated liquid.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) Adding 50mg/L hexadecyl trimethyl ammonium chloride into the concentrated solution in the step (2), heating to 45 ℃, slowly stirring for 45min, performing emulsion breaking treatment, performing cyclone separation treatment, discharging an oil phase from the top, performing biochemical treatment, adding 2% magnesium chloride into a water phase to denature proteins, concentrating by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 100000Da, and drying the concentrated solution to obtain the soluble protein.
Comparative example 1
The difference from example 6 is that: in the step (5), surfactant demulsification treatment is not adopted.
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5-micron organic microfiltration membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 12nm ceramic membrane, concentrating by 23 times, and adding washing water with the volume 2 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing and filtering liquid and penetrating liquid in the step (2) pass through an organic membrane with the molecular weight cutoff of 20000Da, are concentrated to the material concentration of 14 percent, and are added with washing and filtering water with the volume 2 times of that of the concentrated liquid.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) And (3) carrying out cyclone separation treatment on the concentrated solution in the step (2), discharging an oil phase from the top, carrying out biochemical treatment, adding 2% magnesium chloride into a water phase to denature proteins, concentrating by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 100000Da, and drying the concentrated solution to obtain the soluble proteins.
Comparative example 2
The difference from example 6 is that: in step (5), the aqueous phase is not subjected to a protein denaturation treatment with magnesium salts.
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5-micron organic microfiltration membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 12nm ceramic membrane, concentrating by 23 times, and adding washing water with the volume 2 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing and filtering liquid and penetrating liquid in the step (2) pass through an organic membrane with the molecular weight cutoff of 20000Da, are concentrated to the material concentration of 14 percent, and are added with washing and filtering water with the volume 2 times of that of the concentrated liquid.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) Adding 50mg/L hexadecyl trimethyl ammonium chloride into the concentrated solution in the step (2), heating to 45 ℃, slowly stirring for 45min, performing emulsion breaking treatment, performing cyclone separation treatment, discharging an oil phase from the top, performing biochemical treatment, concentrating a water phase by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 100000Da, and drying the concentrated solution to obtain the soluble protein.
Comparative example 3
The differences from example 6 are: the concentrated solution after demulsification is not treated by adopting cyclone separation.
(1) Clarifying sericin wastewater in a silk refining process by adopting a 0.5-micron organic microfiltration membrane, and concentrating after filtering;
(2) and (2) continuously filtering the penetrating fluid obtained in the step (1) by using a 12nm ceramic membrane, concentrating by 23 times, and adding washing water with the volume 2 times that of the concentrated solution for cleaning.
(3) After the washing and filtering are finished, the washing and filtering liquid and penetrating liquid in the step (2) pass through an organic membrane with the molecular weight cutoff of 20000Da, are concentrated to the material concentration of 14 percent, and are added with washing and filtering water with the volume 2 times of that of the concentrated liquid.
(4) And (4) drying the concentrated solution in the step (3) to obtain the micromolecule protein with the highest value.
(5) Adding 50mg/L hexadecyl trimethyl ammonium chloride into the concentrated solution in the step (2), heating to 45 ℃, slowly stirring for 45min, performing emulsion breaking treatment, adding 2% magnesium chloride to denature proteins, concentrating by 15 times through an ultrafiltration membrane with the molecular weight cutoff of 100000Da, and drying the concentrated solution to obtain the soluble proteins.
The cases of the recovered proteins obtained in the above examples and comparative examples are as follows:
note: the recovery rate of the micromolecule protein refers to the content of the recovered micromolecule protein/the content of the protein in the feed liquid before the second ultrafiltration concentration is multiplied by 100 percent; the recovery rate of the water-soluble protein is defined as the content of the recovered water-soluble protein/the content of the protein in the second ultrafiltration concentrate × 100%.
It can be seen from the above table that the method of the present invention can recover and obtain a high degree of small molecule protein, and the comparison between examples 1-3 and examples 4-6 shows that the degree of the recovered water-soluble protein can be significantly improved after the measures of demulsification and cyclone separation are performed on the concentrated solution obtained by the second ultrafiltration process, and the comparison between example 6 and comparative example 1 shows that the dispersibility of emulsified oil droplets can be effectively broken after the measures of demulsification and cyclone separation are performed on the concentrated solution obtained by the second ultrafiltration process, so that the emulsified oil droplets can be more easily removed in the cyclone separation, and the purity of the recovered water-soluble protein is improved, but the processes of cyclone separation and third ultrafiltration are added, so that the recovery rate of the water-soluble protein is reduced; in addition, as can be seen from comparison between example 6 and comparative example 2, the treatment of the aqueous phase solution obtained by the cyclone separation with the addition of an inorganic salt effectively reduced the solubility of the protein, and improved the recovery rate of the protein by the third ultrafiltration membrane. As can be seen from the comparison between example 6 and comparative example 3, the application of the cyclone treatment after the emulsion breaking process can remove more oil droplets from the emulsion breaking process, so as to improve the purity of the recovered protein, but reduce the yield of the recovered protein.
Claims (10)
1. A method for recycling protein wastewater is characterized by comprising the following steps:
step 1, carrying out microfiltration treatment on the protein wastewater;
step 2, performing first ultrafiltration treatment on the microfiltration permeating liquid, and intercepting macromolecular protein;
step 3, carrying out second ultrafiltration treatment on the permeate of the first ultrafiltration, and concentrating the micromolecular protein;
and 4, sequentially concentrating and spray-drying the permeate of the second ultrafiltration to obtain the recovered micromolecule protein.
2. The recycling method of protein wastewater according to claim 1, wherein in one embodiment, a surfactant is added to the first ultrafiltered concentrated solution to perform demulsification treatment, then cyclone separation is performed to remove an oil phase, the water phase is subjected to a third ultrafiltering treatment to concentrate macromolecular proteins, and then the third ultrafiltered concentrated solution is sequentially subjected to concentration and spray drying treatment to obtain water-soluble proteins; in one embodiment, the aqueous phase is treated by a third ultrafiltration after the addition of inorganic salts.
3. The method for recycling protein wastewater as claimed in claim 1, wherein in one embodiment, the surfactant is a cationic surfactant, and the amount of the surfactant can be controlled to be 100-1000 mg/L; in one embodiment, the inorganic salt is a calcium salt or a magnesium salt, and the amount added may be controlled to be 0.5 to 2 wt%.
4. The recycling method of protein wastewater as claimed in claim 1, wherein in one embodiment, the average pore size of the microfiltration membrane during microfiltration is 0.05 to 1.4 μm; in one embodiment, the ultrafiltration membrane of the first ultrafiltration process has an average pore size of 4 to 50 nm; in one embodiment, the ultrafiltration membrane of the second ultrafiltration process has a molecular weight cut-off of 100 to 100000D.
5. The method for recycling protein wastewater according to claim 1, wherein in one embodiment, the ultrafiltration membrane of the third ultrafiltration process has a cut-off molecular weight of 1000 to 300000D.
6. A recycling device of protein waste water, which is characterized by comprising:
the raw material tank (1) is used for storing sericin wastewater;
the microfiltration membrane (2) is connected to the raw material tank (1) and is used for carrying out microfiltration treatment on the sericin wastewater to remove suspended matter impurities;
the first ultrafiltration membrane (3) is connected to the permeation side of the microfiltration membrane (2) and is used for carrying out ultrafiltration, filtration and purification treatment on the filtrate of the microfiltration membrane (2) to remove macromolecular proteins;
the second ultrafiltration membrane (4) is connected to the permeation side of the first ultrafiltration membrane (3) and is used for concentrating the permeation liquid of the first ultrafiltration membrane (3) and intercepting the small-molecule protein;
the concentration device (5) is connected to the interception side of the second ultrafiltration membrane (4) and is used for concentrating the concentrated solution of the second ultrafiltration membrane (4) again;
and the spray drying device (6) is connected to the concentration device (5) and is used for carrying out spray drying treatment on the concentrated solution obtained in the concentration device (5) to obtain the micromolecule protein.
7. The apparatus for recycling protein-containing wastewater as set forth in claim 6, further comprising, in one embodiment: the demulsification reaction tank (7) is connected to the interception side of the first ultrafiltration membrane (3) and is used for performing demulsification reaction treatment on the concentrated solution of the first ultrafiltration membrane (3); the demulsifying reaction tank (7) is also connected with a demulsifying agent adding tank (11); in one embodiment, the demulsifier adding tank (11) is filled with a cationic surfactant; in one embodiment, further comprising: the cyclone separator (8) is connected with the demulsification reaction tank (7) and is used for carrying out cyclone separation treatment on the wastewater obtained in the demulsification reaction tank (7), the oil phase is discharged from the top, and the water phase is discharged from the bottom; in one embodiment, further comprising: the third ultrafiltration membrane (9) is connected with the bottom water phase outlet of the cyclone separator (8) and is used for carrying out protein concentration treatment on the water phase in the cyclone separator (8); in one embodiment, the retentate side of the third ultrafiltration membrane (9) is connected to the concentration device (5).
8. The recycling device of protein wastewater as claimed in claim 6, wherein in one embodiment, the liquid inlet of the third ultrafiltration membrane (9) is further connected with an inorganic salt feeding tank (2); in one embodiment, the top oil phase outlet of the cyclone separator (8) and/or the permeate side of the third ultrafiltration membrane (9) is connected to a biochemical treatment unit (12), the biochemical treatment unit (12) being adapted to perform biochemical treatment on the top oil phase and/or the permeate of the third ultrafiltration membrane (9), respectively; in one embodiment, the average pore size of the microfiltration membrane (2) is 0.05 to 1.4 μm; in one embodiment, the first ultrafiltration membrane (3) has an average pore size of 4 to 50 nm.
9. The recycling device of protein wastewater according to claim 6, wherein in one embodiment, the molecular weight cut-off of the second ultrafiltration membrane (4) is 100-100000D; in one embodiment, the third ultrafiltration membrane (9) has a molecular weight cut-off of 1000 to 300000D.
10. Use of the apparatus for recycling protein waste water according to claim 6 for recycling proteins in waste water.
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