A kind of inoranic membrane or milipore filter regenerating preprocessing agent and preparation method thereof
Technical field
A kind of inoranic membrane or milipore filter regenerating preprocessing agent and preparation method thereof belong to film cleaning and regeneration agent field.Being specifically related to utilize by surfactant, n-nonanoic acid, acetate, hydrogen peroxide and ATMP is that raw material is composite, and the film cleaning and regeneration pretreating agent that ageing makes also relates to the preparation method of this film regenerating preprocessing agent.Water is mixed with the solution that contains this product 0.2%~2.0%, and contaminated inoranic membrane or milipore filter are washed earlier in advance, uses high temperature alkali actified solution cleaning and regeneration subsequently again.
Background technology
Various inoranic membranes or milipore filter are widely used in industries such as food industry, biochemical industry, petrochemical industry, iron and steel, machine-building, mainly concentrate at the macromolecule material, and membrane bioreactor is used in the processing steps such as water-oil separating.In general, because the characteristic of inoranic membrane or milipore filter, itself withstand high temperatures, strong acid, highly basic, peroxide and active chlorine etc., so inoranic membrane or milipore filter regeneration relatively the film of other material than being easier to, has the recovery time weak point, characteristics such as regeneration efficiency height.Just because of these characteristics of inoranic membrane or milipore filter, make people ignore further research, not the potentiality of tap/dip deep into inoranic membrane or milipore filter regeneration efficiency to inoranic membrane or milipore filter regeneration technology.
Traditional inoranic membrane or milipore filter regeneration technology rely on the highly basic of high temperature or the strong acid agent is trapped material as cleaning film surface, fenestra inside and dissolving chemical solution.Be different from organic nanofiltration, the reverse osmosis membrane material is very high to the environmental requirement on contact membranes surface, inorganic material is generally high temperature resistant, the pH scope is wider, and resistance to oxidation and active chlorine.Therefore often use simple industrial chemicals can reach the purpose of regeneration.But existing inoranic membrane or milipore filter regeneration technology also have certain drawback, at first, the activity of alkali in the aqueous solution can increase along with the increase of temperature, most clients improve regeneration temperature as far as possible in regenerative process, this makes irreversibly sex change in regenerative process such as the heat sensitive macromolecular substances of part such as protein or glycoprotein etc., albumen after the polymerization forms dense structure, produces certain resistance for regeneration; Secondly, highly basic and strong acid have certain corrosiveness for other assembly of film device operation, increase the concentration of soda acid simply, improve the temperature of soda acid, may damage associated component, influence pressure, the flow-control of the normal operation of film; At last, active chlorine has certain effect for removing the biological pollution tool, but if do not remove under the clean prerequisite at organic dirt, the existence meeting and the trapped substance of active chlorine forms certain organochlorine and has the material of certain potential toxicity harm for thing etc., has certain risk for food, medicine, Biochemie Gesellschaft m.b.H. (AU) A-6250 Kundl, Austria.
In general, peroxide is all relatively more unstable under high temperature, high-alkali condition, decompose easily and generate organic acid and gas oxygen, and the oxygen that produces in solution can produce the mechanical force that the simple solution ultrafiltration can't produce in fenestra inside in micro-structural fenestra inside, this mechanical force has two kinds of significantly effects, the first, fenestra inside is formed the air-brush effect, directly fenestra is carried out mechanical erosion by newly-generated gas; Second, for the peroxide that is penetrated into trapped substance inside, the release force of explosion that gas produced can significantly destroy the structure of trapped substance after running into highly basic, makes highly basic be more prone to dissolving and dispersion dirt, shorten the recovery time thereby reach, improve the purpose of regeneration efficiency.Yet general trapped substance all can directly react with peroxide, can consume a large portion in peroxide penetrates into the process of trapped substance inside; Peroxide is very unstable under high temperature, high-alkali condition in addition, discharges oxygen rapidly after meeting alkali, concentrate too quickly to discharge gas and can make air scour short action time, and the mechanical force instability.Therefore solving the penetrating power stable and increase peroxide regenerating preprocessing agent of peroxide under high temperature, strong alkali environment is that inoranic membrane or milipore filter regenerating preprocessing agent provide the key of stablizing lasting mechanical force in cleaning process.
Summary of the invention
The object of the invention is to provide a kind of inoranic membrane or milipore filter regenerating preprocessing agent.
Further object of the present invention is to provide the preparation method of this inoranic membrane or milipore filter regenerating preprocessing agent.
This inoranic membrane or milipore filter regenerating preprocessing agent can be widely used in the industries such as food industry, biochemical industry, petrochemical industry, iron and steel, machine-building.
Technical scheme of the present invention: a kind of inoranic membrane or milipore filter regenerating preprocessing agent, be that to be that raw material is composite by surfactant neopelex, n-nonanoic acid, acetate, hydrogen peroxide and ATMP and deionized water make, in concentration expressed in percentage by weight neopelex content 0.05%~0.10% wherein, n-nonanoic acid content 4.0%~6.0%, acetic acid content 20.0%~30.0%; Hydrogen peroxide content 10%~15%, ATMP content 1.5%~2.0%, replenishing with deionized water is 100%.
The preparation method of described inoranic membrane or milipore filter regenerating preprocessing agent according to above-mentioned component prescription, determines the consumption of composite each component, adopts following steps composite:
(1) add acetate in a certain amount of deionized water, add hydrogen peroxide subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water;
(2) in above-mentioned solution, add ATMP, add n-nonanoic acid subsequently, be warming up to 45 ℃ and stir after 30 minutes, reduce to 25 ℃ standby;
(3) in above-mentioned solution, add neopelex again, perfusion after stirring makes its abundant reacted solution deposit 9 days in 30 ± 5 ℃ of environment, packing.
The application of described inoranic membrane or milipore filter regenerating preprocessing agent, be used for food industry, biochemical industry, petrochemical industry, iron and steel, machine industry, be used for the preceding preliminary treatment of inoranic membrane or milipore filter regeneration, with high temperature alkali dissolution liquid to before the film regeneration, elder generation's water is mixed with and contains this regenerating preprocessing agent 0.2%~2.0% solution, wash in advance, carry out conventional high temperature alkali film subsequently again and clean.
Beneficial effect of the present invention: this film regenerative agent of the present invention is, and to be that raw material is composite by surfactant, n-nonanoic acid, acetate, hydrogen peroxide and ATMP make, to inoranic membrane or milipore filter etc. can high-alkali, the strong peroxide of withstand high temperatures and the film of certain mechanical force have good power of regeneration.ATMP can improve the reaction energy threshold of the balanced reaction of hydrogen peroxide and organic carboxyl acid reaction generation peroxide organic carboxyl acid, that is to say that in the system of ATMP existence, hydrogen peroxide and organic carboxyl acid generate the peroxidating organic carboxyl acid and all be subjected to inhibition to the both sides of the balanced reaction speed of development.So, though make product system reach the required time lengthening of balance in the peroxidating organic carboxyl acid preparation process, but the speed that the peroxidating organic carboxyl acid that forms decomposes under high temperature, alkali condition all significantly descends, thereby has improved the stability of peroxide under the high-alkali condition of high temperature.Continue discharging oxygen for this film regenerating preprocessing agent that contains peroxide under alkali condition provides condition, has reduced the initial addition of peroxide, increased the air-brush time, has reduced peroxide and has penetrated into consumption in the trapped substance internal procedure.In addition, in product, added surfactant, surfactant has increased the osmosis of regenerative agent, bring carboxylic acid peroxide and hydrogen peroxide into schmutzband inside, after the actified solution that contains alkali enters dirt inside, the reaction that discharges oxygen occurs in dirt inside, effectively destroys the structure of trapped substance.Not only make the film recovery time shorten, the film regeneration effect improves, and has prolonged the service life of film.The product that makes with the present invention is regenerated with high temperature alkali dissolution liquid after contaminated inoranic membrane or milipore filter are washed earlier in advance again, can remove in the fenestra rapidly and film is surperficial holds back material, significantly increases the film regeneration efficiency.The present invention utilizes ATMP as peroxide organic acid stabilizing agent, makes the newborn oxygen of compound peroxide slowly-releasing under high temperature, high-alkali condition, the mechanical force that the peroxide aerogenesis is produced under the control micro.In regenerative process, can effectively destroy the compact texture of trapped substance, quicken the speed of alkali dissolving dirt, make the control of aerogenesis mechanical force within the specific limits simultaneously again, can not damage membrane material.Have following outstanding advantage:
1, the film reproduction speed significantly increases, for dissolving, the dispersibility enhancing of organic trapped substance;
2, the long-term use keeps the penetrating amount of film to be stabilized in higher level;
3, film regeneration efficiency height.
Description of drawings
Fig. 1 peroxide organic acid content downward trend figure.
The stable tendency chart of Fig. 2 peroxide organic acid in hot alkaline solution.
Fig. 3 shortens the tendency chart of film recovery time.
The specific embodiment
Embodiment 1
Get adding 1000g acetate in the 1500g deionized water, add 1000g (50% hydrogen peroxide) subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water; In above-mentioned solution, add the 100.0g ATMP and add about 300g n-nonanoic acid subsequently, be warming up to 45 ℃ of stir abouts after 30 minutes, reduce to 25 ℃ standby; Solution after cooling adds about 5.0g neopelex, and adding deionized water control gross mass again is 5000g, and the solution after stirring pours into, obtains finished product 1 deposit 9 days in 30 ± 5 ℃ of environment after.
Get adding 1300g acetate in the 1600g deionized water, add 1000g (50% hydrogen peroxide) subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water; Be warming up to 45 ℃ of stir abouts after 30 minutes, reduce to 25 ℃ standby; Solution after cooling adds about 5.0g neopelex, and adding deionized water control gross mass again is 5000g, and the solution after stirring pours into, obtains peracetic acid soln A deposit 9 days in 30 ± 5 ℃ of environment after.
Detect peroxide organic acid content among finished product 1 and the peracetic acid soln A respectively with iodimetric titration, with this content as 100%, again finished product 1 and peracetic acid soln A are positioned over constant temperature in 60 ℃ of environment, detected two kinds of peroxide organic acid content and records in the solution every 24 hours respectively with iodimetric titration, after the continuous detecting 30 days, the result and the preceding two kinds of solution peroxide organic acid contents of insulation that detect are contrasted at every turn, and peroxide organic acid content downward trend is seen Fig. 1.
As can be seen from Figure 1, in same temperature, under the storage condition, the peroxide organic acid of the present invention preparation is with after the peroxide organic acid of conventional method preparation is placed identical fate, and tradition is crossed acid content and dropped to about 25% of initial concentration; And the acid content of crossing of the present invention maintains more than 75% of initial content.Illustrate that the more traditional peracid of peroxide organic acid heat endurance among the present invention is good.
Embodiment 2
Get adding 1500g acetate in the 1500g deionized water, add 1500g (50% hydrogen peroxide) subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water; In above-mentioned solution, add the 75.0g ATMP and add about 200g n-nonanoic acid subsequently, be warming up to 45 ℃ of stir abouts after 30 minutes, reduce to 25 ℃ standby; Solution after cooling adds about 2.5g neopelex, and adding deionized water control gross mass again is 5000g, and the solution after stirring pours into, obtains finished product 3 deposit 9 days in 30 ± 5 ℃ of environment after.
Get adding 1500g acetate in the 1200g deionized water, add 1250g (50% hydrogen peroxide) subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water; Be warming up to 45 ℃ of stir abouts after 30 minutes, reduce to 25 ℃ standby; Solution after cooling adds about 3.7g neopelex, and adding deionized water control gross mass again is 5000g, and the solution after stirring pours into, obtains peracetic acid soln B deposit 9 days in 30 ± 5 ℃ of environment after.
Getting the direct respectively solution 995ml that injects two parts 40 ℃ sodium hydrate content about 4.0% of 5ml finished product 2 and peracetic acid soln B fully stirs, every 3 minutes above-mentioned solution is taken a sample respectively, solution after the sampling is immediately with phosphoric acid neutralization alkali wherein, detect peroxide organic acid content and the record that contains in finished product 2 and the peracetic acid soln B solution respectively with iodimetric titration again, after the continuous detecting 30 minutes, with the result that at every turn detects and add the preceding two kinds of solution of heat alkali liquid on year-on-year basis the peroxide organic acid content contrast, the stable trend of peroxide organic acid in hot alkaline solution is seen Fig. 2.
As can be seen, the peracid of the peracid of the present invention's preparation and conventional method preparation is injecting uniform temp from above-mentioned data, and in the solution of basicity, traditional peracid content after about 12 minutes promptly decays to below 20% of initial content.The peracid of the present invention's preparation still kept after 30 minutes more than 70%, illustrated that the stability of peracid under the alkali environment of the present invention's preparation is better than traditional peracid.The effective newborn oxygen of slowly-releasing in the film regenerative process provides lasting mechanical force.
Embodiment 3
Get adding 1250g acetate in the 1500g deionized water, add 1250g (50% hydrogen peroxide) subsequently again, stirring makes acetate and hydrogen peroxide dissolve fully in water; In above-mentioned solution, add the 88.0g ATMP and add about 250g n-nonanoic acid subsequently, be warming up to 45 ℃ of stir abouts after 30 minutes, reduce to 25 ℃ standby; Solution after cooling adds about 3.7g neopelex, and adding deionized water control gross mass again is 5000g, and the solution after stirring pours into, obtains finished product 3 deposit 9 days in 30 ± 5 ℃ of environment after.
Contain the aqueous solution of finished product 3 about 0.5% as regenerating preprocessing agent with the deionized water preparation, to filtering the pre-flushing 10 minutes of pressurizeing of the about 7 hours nanofiltration membrane of extract solution from aloe, after the pre-flushing, regenerate with 4.0% sodium hydroxide solution again, this film water purification flux drops to 37% of design flux before the regeneration, cleaning temperature is controlled at 45 ℃, and the penetrating amount of solution reaches about 35 minutes of the 85% o'clock used time (containing pre-washing time) of design flux.
Contain the aqueous solution of NaOH about 4.0% as regenerative agent with the deionized water preparation, carry out pressure flush to filtering the about 7 hours nanofiltration membrane of extract solution from aloe, this film water purification flux drops to 44% of design flux before the regeneration, cleaning temperature is controlled at 45 ℃, and the penetrating amount of solution reaches about 170 minutes of the 85% o'clock used time of design flux.
Shorten the trend of film recovery time and see Fig. 3.As can be seen from Figure 3, under all identical situation of temperature, time, basicity, before the regeneration under the approaching situation of membrane flux, with the pretreated inoranic membrane of the present invention, membrane flux with the regeneration of high temperature alkali reaches 85% of design flux again, about 40 minutes of time, and traditional alkali needs about 170 minutes; Illustrate that the more traditional alkali of the present invention can significantly improve regeneration efficiency, reduce the recovery time.