CN115025630A

CN115025630A - Preparation method and product of hollow cellulose virus removal filtering membrane

Info

Publication number: CN115025630A
Application number: CN202210621813.7A
Authority: CN
Inventors: 不公告发明人
Original assignee: Sepp Hangzhou Filtration Technology Co ltd
Current assignee: Sepp Hangzhou Filtration Technology Co ltd
Priority date: 2021-06-02
Filing date: 2022-06-01
Publication date: 2022-09-09

Abstract

The invention discloses a preparation method of a hollow cellulose virus-removing filter membrane, which comprises the following steps: (1) uniformly mixing esterified cellulose, a pore-forming component and a mixed solvent, and filtering and defoaming to obtain a spinning solution; (2) spinning solution in the outer nozzle and core solution in the inner nozzle are sprayed out by a spinning nozzle to enter a coagulating bath filled with coagulating liquid, and the solidified hollow membrane is continuously collected; (3) and hydrolyzing the solidified hollow membrane to obtain the regenerated hollow fiber membrane. The invention also provides a hollow cellulose virus removal filter membrane product. The raw materials adopted by the invention are natural and hydrophilic, the protein adsorption is extremely low, the preparation process is simple, and the subsequent treatment is not needed. The method of the invention can control the section structure, and the controllable structure can greatly increase the selectivity of the filtering material liquid, inhibit the blockage caused by filtering and improve the filtering performance.

Description

Preparation method and product of hollow cellulose virus removal filtering membrane

Technical Field

The invention belongs to the technical field of virus removal, and particularly relates to a preparation method and a product of a hollow cellulose virus removal filtering membrane.

Background

Virus removal is a very important process step in the biopharmaceutical industry, the blood products industry or in the field of recombinant proteins. The adoption of a virus filtering membrane is an effective method which can not cause protein modification and can reduce viruses. Due to the excellent hydrophilic property of the cellulose, no post-treatment modification is needed, the protein adsorption is extremely low, the flux is faster than that of a PVDF membrane, and the cellulose virus removal filtering membrane is a widely used virus removal filtering membrane at present.

For example, patent document CN108602026A discloses a virus-removing membrane and a method for producing a virus-removing membrane, which comprises dissolving cellulose in a cuprammonium solution, adding a silicate to the solution to form a dope, aging the dope, and subjecting the dope to microphase separation and solidification in a coagulation solution containing ammonia water to obtain a virus-removing fiber filtration membrane. The method has many problems, on one hand, the adoption of the copper ammonia solution has large pollution and large difficulty in recovery and post-treatment, and meanwhile, the method needs to strictly control the parameters of the process.

Patent document No. CN105980038B also discloses a hollow fiber membrane, which is prepared by dissolving cellulose in cuprammonium solution, and has similar technical problems. And the controllability is poor.

Patent document CN 105980037B discloses a hollow virus-removing membrane prepared by using polyvinylidene fluoride resin. However, these hydrophobic thermoplastic crystalline resins tend to cause adsorption of proteins and the like, fouling of the membrane, clogging and the like, and cause a rapid decrease in filtration rate. Therefore, when a hydrophobic resin is used as a material for a virus-removing membrane, the membrane needs to be modified to have hydrophilicity in order to prevent blocking due to adsorption of proteins and the like. Such as grafted chains that impart hydrophilicity to the membrane by graft polymerization. The structural film has poor biodegradability on one side, cannot be recycled, and has a complex preparation process.

Disclosure of Invention

The invention provides a preparation method of a hollow cellulose virus-removing filtering membrane, which is simple in process, strong in controllability and capable of avoiding the adoption of a serious-pollution cuprammonium solution.

Meanwhile, the invention also provides the hollow fiber membrane prepared by the preparation method, the hollow fiber membrane has good biodegradability and can be recycled, and the performance of the hollow fiber membrane meets the virus filtration requirement.

A preparation method of a hollow cellulose virus removal filtering membrane comprises the following steps:

(1) uniformly mixing esterified cellulose, pore-forming components and a mixed solvent, and filtering and defoaming to obtain a spinning solution;

(2) spraying the spinning solution in the outer nozzle and the core solution in the inner nozzle into a coagulating bath by using a spinning nozzle, and continuously collecting the solidified hollow membrane to obtain a solidified hollow membrane;

(3) and hydrolyzing the solidified hollow membrane to obtain the regenerated hollow fiber membrane.

Preferably, the esterified cellulose, the pore-forming component and the mixed solvent in the step (1) comprise the following components in percentage by weight:

12 to 30 percent of esterified cellulose

20 to 45 percent of pore-forming component

35-60% of mixed solvent.

Preferably, the esterified cellulose accounts for 15 to 25 percent by weight; more preferably 16 to 21%. The weight percentage content of the pore-forming component is 23% -35%, and the even better preference is 23% -30%. The weight percentage content of the mixed solvent is 50% -60%, and more preferably 55% -58%.

Preferably, the pore-forming component comprises a pore-forming component A accounting for 0.1-5% of the weight of the total component (esterified cellulose, pore-forming component and mixed solvent) and a pore-forming component B accounting for 20-40%; preferably, the pore-forming component comprises a pore-forming component A accounting for 0.1 to 1.5 percent of the total weight of the components and a pore-forming component B accounting for 20 to 30 percent of the total weight of the components; more preferably, the pore-forming component comprises a pore-forming component A accounting for 0.1-1% of the total weight of the components and a pore-forming component B accounting for 20-25% of the total weight of the components. The pore-forming component A is selected from one or more of polyvinylpyrrolidone, polyethylene glycol and water; the pore-forming component B is selected from one or two of formamide and acetamide.

Preferably, the mixed solvent comprises a volatile solvent and a non-volatile solvent; the volatile solvent is selected from one or more of acetone and dioxane; the non-volatile solvent is selected from one or more of dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide; the non-volatile solvent is further preferably dimethylacetamide and dimethyl sulfoxide, and the ratio of dimethylacetamide to dimethyl sulfoxide is preferably 5-15: 1. Preferably, the mixed solvent comprises a volatile solvent accounting for 20-30% of the total weight of the components and a non-volatile solvent accounting for 15-30% of the total weight of the components. As a further preference, the mixed solvent comprises a volatile solvent accounting for 25-30% of the total weight of the components and a non-volatile solvent accounting for 25-30% of the total weight of the components. As a further preference, the mixed solvent comprises a volatile solvent accounting for 27-30% of the total weight of the components and a non-volatile solvent accounting for 28-30% of the total weight of the components.

Preferably, the esterified cellulose is selected from one or more of cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate phthalate, cellulose acetate butyrate, and cellulose acetate propionate.

Preferably, in the step (1), the mixing temperature is 30 to 80 ℃, and more preferably 40 to 80 ℃.

By adjusting the material proportion in the step (1), regenerated cellulose virus-removing flat filter membranes with different average pore diameters can be obtained.

Preferably, in the step (1), the material spraying speed of the spinning solution in the outer spray head is 1-5 ml/min. Further preferably 1 to 2 ml/min. The material spraying speed of the core liquid in the inner spray head is 1.5-10 ml/min; further preferably 2 to 3 ml/min.

Preferably, the invention can adjust the distance between the spinneret and the coagulation bath in the step (2) to regulate the contact time of the spinning solution and air, thereby realizing the pre-forming of the spinning solution. The pore size and distribution in the preformed spinning solution are regulated and controlled by controlling the air humidity and/or the air wind speed or the air residence time. The greater the air humidity, the greater the air velocity, the longer the residence time, the greater the degree of vapor intrusion in volatile exchange with the volatile solvent, the larger the surface openings, and the higher the macroporous layer fraction as seen from the cross-sectional layer. The macroporous layer ratio can affect the strength of the membrane, the porosity of the membrane, the virus interception efficiency and the permeability of igg.

Preferably, the air humidity is 60% -95%; the air speed is 0.2m/min-0.5 m/min; the height of the air section is 3-20 cm; the residence time in the air section is between 0.2s and 10 s. More preferably, the air humidity is 75% -90%; the air speed is 0.1-1 m/min; the residence time is 0.2-0.5 s. The humidity is increased, the residence time is increased, and the wind speed is increased, which are beneficial to the reduction of the thickness of the compact layer, the reduction of the stretching force and the increase of the flow speed.

According to the invention, the composition and temperature of the core liquid and the solidification liquid are adjusted, and the surface tension and mass transfer speed of the core liquid and the solidification liquid system are adjusted, so that the regulation and control on the pore size and distribution of the inner surface and the outer surface of the hollow membrane, the relative position of the compact layer and the like are realized. Generally, the surface tension of the core liquid and coagulation bath system is less than 21mN.m ^-1 Since the exchange rate between substances is reduced, the phase separation speed is reduced, the curing and forming time of the film is increased, and the normal production is not facilitated. The surface tension of the core liquid and the coagulating bath system is more than 28.9mN.m ^-1 The inner surface or the outer surface is easy to form a skin layer structure, and the thickness range of the skin layer small hole structure is formedAt 100-300nm, the pore size is in the range of 1k-100k, which is not favorable for filtering the virus. The phase separation speed of substances is different under different surface tension or temperature conditions. The higher the tension is, the higher the temperature is, the faster the exchange speed of the spinning solution with the core solution and the coagulating bath is, the faster the phase separation is, the shorter the surface layer curing time is, the pore layer is formed, and the exchange speed of the spinning solution below the surface layer is obstructed due to the pores on the surface layer, so that the macropores are formed.

In the present invention, the coagulation bath comprises between 10% and 60% by weight of a high surface tension solvent and between 40% and 90% by weight of a low surface tension solvent. As a further preference, the coagulation bath comprises between 30% and 60% by weight of a high surface tension solvent and between 40% and 70% by weight of a low surface tension solvent; as a still further preference, the coagulation bath comprises between 50% and 60% by weight of a high surface tension solvent and 40% to 50% by weight of a low surface tension solvent. The bore fluid comprises 10-60% by weight of a high surface tension solvent and 40-90% by weight of a low surface tension solvent. As a further preference, the bore fluid comprises between 30% and 60% by weight of a high surface tension solvent and 40% to 70% by weight of a low surface tension solvent; as a still further preference, the bore fluid comprises between 40% and 50% by weight of a high surface tension solvent and between 50% and 60% by weight of a low surface tension solvent.

The surface tension of the core liquid or coagulating bath system is controlled to be 21mN.m ^-1 -28.9mN.m ^-1 To (c) to (d); preferably, the surface tension of the coagulation bath system is controlled to 23mN.m ^-1 -28.9mN.m ^-1 To (c) to (d); the surface tension of the core liquid is controlled to be 22mN.m ^-1 -25mN.m ^-1 To (c) to (d); or the core liquid is compressed nitrogen, and the flow rate is controlled to be 5-20ml/min, so that the residue of the traditional core liquid in the membrane filaments is mainly avoided.

Preferably, the residence time of the hollow membrane in the coagulation bath is 10 to 200 seconds, and more preferably 50 to 100 seconds.

Preferably, the temperature of the coagulation bath is 15 ℃ to 30 ℃ at the time of curing, and more preferably 15 ℃ to 27 ℃. The temperature of the core liquid is 20-30 ℃, and the more preferable temperature is 20-27 ℃.

Preferably, the high surface tension solvent is water; the low surface tension solvent is any mixture of methanol, ethanol and isopropanol or one of the three.

Preferably, the cured hollow membrane has a structure in which the inner-side to outer-side pore diameter is reduced; or the solidified hollow membrane has a structure that the inner side increases towards the outer aperture; or the solidified membrane is a structure with the aperture decreasing from two sides to the middle.

Preferably, the hollow membrane continuous collection can be realized by adopting a wire collecting device with a winding mechanism. The winding speed is generally consistent with the curing speed, and the cured hollow membrane is collected in real time. The winding speed is generally controlled to be 5m/min-25 m/min.

Preferably, the hydrolysis is carried out in an alkaline solution, the concentration of the alkaline solution is 0.01-1 mol/L, and the regenerated cellulose membrane after hydrolysis is cleaned, moisturized and dried to obtain the regenerated cellulose virus-removing filter membrane. When the hydrolysis process is carried out, the wound hollow membrane can be directly placed into alkali liquor, and after the hollow membrane is hydrolyzed, the wound hollow membrane can be taken out and subjected to post-treatment to obtain the regenerated hollow fiber membrane.

In the hydrolysis process, the higher the hydrolysis concentration, the shorter the time required to obtain regenerated cellulose, the higher the hydrolysis temperature, which is in the range of 30-80 ℃, and the shorter the time to obtain regenerated cellulose. The final characterization was verified by infrared until the carbonyl peak of cellulose acetate was 1740cm ^-1 Completely disappears to obtain the complete regenerated cellulose.

And (3) cleaning, moisturizing and drying the hydrolyzed regenerated cellulose membrane to obtain the regenerated cellulose virus removal filter membrane.

A hollow fiber membrane is prepared by the preparation method of the hollow cellulose virus-removing filter membrane, wherein the average pore diameter of a dense layer in the filter membrane is 10-40nm, more preferably 15-30nm, and still more preferably 18-23 nm; in the present invention, the "dense layer" refers to a membrane layer that mainly functions to remove viruses by filtration, and may be referred to as a "dense layer". The thickness of the precision layer is 15-60 μm; more preferably 25 to 40 μm.

Preferably, the thickness of the film in the dry state is from 30 μm to 70 μm. The outer diameter (diameter) is 300 μm to 600 μm. The inner diameter (diameter) is 300 μm to 600. mu.m.

More preferably, the film thickness is 35 μm to 50 μm in a dry state. The outer diameter is 400-500 μm. The inner diameter is 350-450 μm.

Preferably, the regenerated hollow fiber membrane has a structure in which the pore diameter decreases from a first side to a second side, and the first side or the second side may be the inside of the hollow fiber membrane or the outside of the hollow fiber membrane. The size of the first side surface hole is 0.5-2.5 μm; the size of the second side surface hole is 0.01-1 μm.

Compared with the prior art, the hollow regenerated cellulose virus removal filter membrane has the advantages that: 1. the regenerated cellulose as the raw material is natural and hydrophilic, the protein adsorption is extremely low, the preparation process is simple, and the subsequent treatment is not needed. 2. The preparation method of the regenerated cellulose virus-removing filtering membrane ensures that the cross section structure is controllable, the controllable structure greatly increases the selectivity of the filtering material liquid, the blockage accompanying the filtering is inhibited, and the filtering performance is improved. 3. The thick precision filter layer (the compact layer increases the stability of the product quality and improves the virus removal rate 4. under the condition of ensuring the virus removal, the high flux greatly improves the process time of the process.

Drawings

FIG. 1, FIG. 2 and FIG. 3 are graphs showing the infrared contrast of the regenerated cellulose prepared in example 1 before, during and after hydrolysis of the virus-removing filtration membrane, respectively.

Fig. 4 and 5 are scanning electron micrographs of the inner surface and the outer surface of the film product corresponding to example 1 after metal spraying, respectively.

Detailed Description

In order that the above objects, features and advantages of the present invention can be more clearly understood, a more particular description of the invention will be rendered by reference to the appended drawings. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.

In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and therefore the scope of the present invention is not limited by the specific embodiments disclosed below.

Examples 1 to 5

A preparation method of a hollow membrane of a regenerated cellulose virus-removing filter membrane comprises the following steps:

s1: cellulose diacetate films were provided as starting materials. In this example, the total amount of the material is 20kg, and 16.5% of cellulose diacetate, 1% of pore-forming component a: polyvinylpyrrolidone K30, 25% of pore-forming component B: acetamide, 29.5% of a conventional volatile solvent A acetone, 26% of a conventional non-volatile solvent B dimethylacetamide and 2% of dimethylsulfoxide. And uniformly mixing the raw materials at 40-50 ℃, and filtering and defoaming to obtain the spinning solution.

S2: then, the spinning solution is sprayed out from an outer nozzle of a spinneret by a spinning pump at the speed of 1.6ml/min into a coagulating bath (50% isopropanol aqueous solution at 20 ℃), and a core solution (50% isopropanol aqueous solution at 27 ℃) is also sprayed out from an inner nozzle of the spinneret at the speed of 2.6ml/min simultaneously, wherein the outer nozzle of the spinneret has the size of 0.6mm of outer diameter and 0.4mm of inner diameter; the height of the air section is 5cm (the air humidity is 80 percent, the air wind speed is 0.5m/min), the residence time is 0.33s, the spinning speed is 9m/min, the average residence time of the spinning solution is ensured to be 60s, and the hollow membrane is continuously solidified and discharged. Hydrolyzing the solidified hollow membrane in 0.05m/L sodium hydroxide solution at 50 deg.C for 10 hr, and performing infrared verification (as shown in FIGS. 1-3, FIG. 1 is an infrared spectrum of the solidified hollow membrane before hydrolysis, FIG. 2 is an infrared spectrum of the solidified hollow membrane during hydrolysis (5 hr), and FIG. 3 is an infrared spectrum of the hydrolysis), wherein the carbonyl peak of cellulose acetate is 1740cm ^-1 Completely disappeared to obtain a complete regenerated cellulose membrane. (the hollow cellulose size of 480 micron outer diameter, wall thickness 45 micron, inner diameter 390 micron)

S3: and (3) cleaning, namely cleaning the hydrolyzed finished membrane, soaking the cleaned regenerated cellulose membrane in a 20% glycerol aqueous solution, moisturizing, and drying. The final dried film had an outer diameter of 460 μm, a wall thickness of 40 μm and an inner diameter of 380 μm. Fig. 4 and 5 are scanning electron micrographs of the inner surface and the outer surface of the film product corresponding to example 1 after metal spraying, respectively.

The total material was unchanged, and the composition of the material was changed to obtain hollow regenerated cellulose membranes of different pore sizes, to obtain examples 2-5, see table 1:

TABLE 1

Note: the values to the left of "+" in solvent B represent the percent of dimethylacetamide and the values to the right of "+" represent the percent of dimethylsulfoxide.

Examples 6 to 9

The total material is 20kg, 19.2% of cellulose diacetate is selected as a raw material, 0.7% of pore-forming agent A component PVP-K30, 24% of pore-forming agent B component acetamide, 28.1% of solvent A acetone, 26% of solvent B dimethylacetamide and 2% of dimethyl sulfoxide are selected. The spinning solution was discharged from the outer nozzle of the spinneret at a rate of 1.5ml/min by a spinning pump into different coagulation baths and coagulation bath temperatures of 2, and simultaneously discharged from the inner nozzle of the spinneret at a rate of 2.3ml/min using different core solutions and different core solution temperatures (see table 2), and the other processes were the same as in example 4.

TABLE 2

Examples 10 to 12

The same conditions as in example 4 were followed, except that the cellulose diacetate in example 4 was replaced with an esterified cellulose as in Table 3:

TABLE 3

Examples	Esterified cellulose
		10	Cellulose triacetate
11	Cellulose propionate
		12	Cellulose acetate butyrate

Performance detection

Average pore size (nm), bubble pressure (MPa), flow rate (LMH/bar), dense layer thickness (μm), tensile strength (N), protein permeability (%), virus retention (LRV), outer surface pore size (nm), inner surface pore size (nm) measurements, see table 5:

the detection methods are respectively as follows:

average pore diameter test: the test was carried out with a pore size distribution tester PMI, cutting a membrane of a certain size and then applying a low surface tension (15.6mN. m.) ^-1 N/m) solvent (supplied by PMI equipment, usa) was wetted, then placed in test cells, and finally the mean pore size and the bubble-starting pore size were obtained by a dry-wet line.

And (3) bubble pressure test: the obtained film was coated with a low surface tension liquid of 13.6mN.m ^-1 (3M ^TM Novec ^TM 7100) After wetting, the membrane was slowly pressurized with compressed nitrogen until continuous bubbles were formed on the membrane surface, at which time the gas pressure was referred to as the bubble pressure (MPa).

Flow rate: the results were obtained using a Millipore Virusmax test apparatus plus a 25mm stainless steel replaceable membrane filter (both protein permeability and viral filtration experiments were carried out using this apparatus) with an effective filtration area of 4.1cm ² Using ultrapure water with the temperature of 25 ℃, controlling the pressure to be 2barAnd (5) performing line filtration test.

And (3) testing the thickness of the compact layer: the thickness of the dense layer was measured by SEM cross-sectional view.

Testing of tensile strength: the film cutter is used for cutting a test sample into small film pieces with the width of 1cm and the length of 8-10cm, and the microcomputer control electronic universal tester LD22.501 is used for testing the tensile strength within the range of 0-50N.

Protein transmittance test: igg protein solution (such as 1g/L, 5g/L, etc.) with certain concentration is prepared, and pre-filtering is carried out to remove particles and prepolymer of the protein solution with the particle size of 0.22 mu m. The measurement was also carried out using a Virusmax measuring apparatus from Millipore plus a 25mm stainless steel membrane filter, and the absorbance was measured at a wavelength of 280nm using an ultraviolet spectrophotometer UV-5 (manufactured by Mettler). The transmittance calculation formula is as follows:

transmittance of C ₁ /C ₀ ×100％，C ₁ As permeate concentration, C ₀ Is the stock solution concentration.

Virus retention experimental testing: using polyclonal IgG as an antibody solution, 5% of MVM murine parvovirus (size 18-24nm) and BVDV (size 50-70nm) were added to the obtained antibody solution, and the mixture was thoroughly stirred to obtain a virus-containing antibody solution. The tests were carried out using a Virusmax test apparatus from Millipore plus a 25mm stainless steel membrane change filter:

LRV＝log ₁₀ (C0/CF)

c0 represents the infectious titer of the stock solution containing the antibody against the virus, and CF represents the infectious titer in the filtrate obtained by removing the virus filtration membrane using regenerated cellulose.

Detecting the sizes of the outer surface hole and the inner surface hole: the surface and bottom surface hole test methods also take SEM pictures for measurement.

TABLE 5

From examples 1 to 5 and the above test data, it can be known that the regenerated cellulose membranes with different pore diameters can be obtained by changing the composition of the material in step S1, which fully indicates that the method of the present invention has strong controllability, and can select an appropriate process according to the size of the virus to be removed to obtain an appropriate membrane product.

From examples 6 to 9 and the above test data, it can be seen that the pore size distribution on the outer surface was controlled by adjusting the composition and temperature of the coagulation bath. The size distribution of the inner surface pores is regulated and controlled by adjusting the composition and the temperature of the core liquid. The position distribution of the compact layer relative to the inner and outer surfaces is regulated and controlled by adjusting the composition/temperature of the coagulating bath and the composition/temperature of the core liquid.

From examples 10 to 12 and the above test data, it can be seen that the use of different esterified celluloses also has an effect on the average pore size and the pore size distribution of the inner and outer surfaces.

Claims

1. A method for preparing a hollow cellulose virus removal filtering membrane is characterized by comprising the following steps:

(1) uniformly mixing esterified cellulose, a pore-forming component and a mixed solvent, and filtering and defoaming to obtain a spinning solution;

(2) spinning solution in the outer nozzle and core solution in the inner nozzle are sprayed into a coagulating bath filled with coagulating liquid by using a spinning nozzle, and the solidified hollow membrane is continuously collected;

2. The method for preparing a hollow cellulose virus-removing filtration membrane according to claim 1, wherein the pore sizes and distributions of the inner surface and the outer surface of the hollow membrane are controlled by adjusting the surface tensions of the core solution and the coagulating solution.

3. The method for preparing a hollow cellulose virus-removing filtration membrane according to claim 1, wherein the bore fluid or the coagulating fluid comprises 10-50% by weight of a high surface tension solvent and 50-90% by weight of a low surface tension solvent; the surface tension of the core liquid or the coagulating bath system is controlled to be 21-28.9mN.m ^-1 To (c) to (d); alternatively, the bore fluid is a gas.

4. The method for producing a hollow cellulose virus removal filtration membrane according to claim 3, wherein the high surface tension solvent is water; the low surface tension solvent is any mixture of methanol, ethanol and isopropanol or one of the three.

5. The preparation method of the hollow cellulose virus-removing filter membrane according to claim 1, wherein the esterified cellulose, the pore-forming component and the mixed solvent in the step (1) comprise the following components in percentage by weight:

12 to 30 percent of esterified cellulose

20 to 45 percent of pore-forming component

35-60% of mixed solvent.

6. The preparation method of the hollow cellulose virus-removing filtering membrane according to claim 1, wherein the pore-forming component comprises a pore-forming component A accounting for 0.1-5% of the total weight of the component and a pore-forming component B accounting for 20-40% of the total weight of the component; the pore-forming component A is selected from one or more of polyvinylpyrrolidone, polyethylene glycol and water; the pore-forming component B is selected from one or two of formamide and acetamide.

7. The method for producing a hollow cellulose virus removal filtration membrane according to claim 1, wherein the mixed solvent contains a volatile solvent and a non-volatile solvent; the volatile solvent is selected from one or more of acetone and dioxane; the non-volatile solvent is selected from one or more of N-methylpyrrolidone, dimethylacetamide, N-dimethylformamide and dimethyl sulfoxide.

8. The method of claim 1, wherein the esterified cellulose is selected from the group consisting of cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose acetate phthalate, cellulose acetate butyrate, and cellulose acetate propionate.

9. The method of producing a hollow cellulose virucidal filtration membrane according to claim 1, wherein the solidified hollow membrane has a structure in which the pore diameter decreases from the inside to the outside in the thickness direction; or the solidified hollow membrane is of a structure with the inner side and the outer side with the aperture increased; or the solidified hollow membrane is in a structure with the pore diameter decreasing from two sides to the middle.

10. The method for preparing a hollow cellulose virus-removing filtration membrane according to claim 1, wherein the hydrolysis is carried out in an alkaline solution, the concentration of the alkaline solution is 0.01mol/L to 1mol/L, and the hydrolyzed regenerated cellulose membrane is washed, moisturized and dried to obtain the regenerated cellulose virus-removing filtration membrane.

11. A hollow cellulose virus-removing filtration membrane, which is produced by the production method for a hollow cellulose virus-removing filtration membrane according to any one of claims 1 to 10, wherein the average pore diameter of a dense layer in the filtration membrane is 10 to 40 nm; the thickness of the film in a dry state is 30 to 70 μm, and the outer diameter is 300 to 600 μm.