CN115770487A - Peroxide composite sustained-release tablet and preparation method and application thereof - Google Patents
Peroxide composite sustained-release tablet and preparation method and application thereof Download PDFInfo
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- CN115770487A CN115770487A CN202211485922.7A CN202211485922A CN115770487A CN 115770487 A CN115770487 A CN 115770487A CN 202211485922 A CN202211485922 A CN 202211485922A CN 115770487 A CN115770487 A CN 115770487A
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- Prior art keywords
- peroxide
- release tablet
- solid
- parts
- acid
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- 150000002978 peroxides Chemical class 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000007939 sustained release tablet Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 103
- 239000007787 solid Substances 0.000 claims abstract description 63
- 238000004140 cleaning Methods 0.000 claims abstract description 52
- 239000003826 tablet Substances 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 36
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000004021 humic acid Substances 0.000 claims abstract description 33
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- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims abstract description 19
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
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- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 3
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- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 2
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- 229930006000 Sucrose Natural products 0.000 claims description 2
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- Detergent Compositions (AREA)
Abstract
A peroxide composite sustained-release tablet, a preparation method and application thereof, relating to the technical field of membrane pollution cleaning tablets. The object of the present invention is to solve OH for efficient membrane cleaning · The high reactivity to the target compound and the organic/inorganic components competing in water and self-quenching by radical chain reaction may cause a problem of poor catalytic durability. The method comprises the following steps: under the dry condition, solid peroxide, catalytic assistant, solid weak acid, lubricant, water absorbing material and tetraacetylethylenediamine are mixed uniformly and then tabletted. Filtering humic acid solution by using an ultrafiltration membrane for 2-100 h, then immersing the ultrafiltration membrane into water, adding a solid peroxide composite slow-release tablet, and then circularly cleaning the ultrafiltration membrane attached with the humic acid for 3-30 min. The invention can obtain a peroxide composite sustained-release tablet and a preparation method and application thereof.
Description
Technical Field
The invention relates to the technical field of membrane pollution cleaning tablets, in particular to a preparation method of a solid calcium peroxide composite sustained-release tablet and a method for cleaning an ultrafiltration membrane in situ by using the tablet.
Background
The pre-oxidation Ultrafiltration (UF) process HAs proven to be an efficient and robust process with high removal of Humic Acid (HA), F, compared to traditional water treatment processese 2+ (Mn 2+ ) And low chemical consumption. In the long-term separation process, membrane pollutants Humic Acid (HA) and FeO x +MnO x In combination, can lead to severe irreversible membrane fouling, thereby reducing the effectiveness and sustainability of membrane filtration. However, the mass transfer rate of the active ingredients for removing irreversible pollutants by acid washing and alkali washing is low, and the problems of long soaking time and large chemical consumption exist. Sodium hypochlorite (NaClO) is a common oxidant for membrane cleaning, but high chlorine doses lead to the formation of halogenated byproducts during chemical cleaning of HA-contaminated membranes and enhance the potential for faster scale development.
As a green oxidizing agent, hydrogen peroxide (H) 2 O 2 ) Radicals can be generated as precursors by fenton-like reactions, and radicals with high redox potentials can change hydrophobic irreversible contaminants into more hydrophilic species that are more easily removed from the membrane surface by subsequent physicochemical processes. The hydrogen peroxide is an inorganic substance and belongs to a stronger oxidant, and the acidic condition is favorable for the stability of the hydrogen peroxide; meanwhile, the hydrogen peroxide is an efficient disinfectant and bactericide, and is widely applied to the fields of wound disinfection, environment and food disinfection and the like. Compared with chlorine cleaning agents (such as NaClO), the hydrogen peroxide has the advantages of less using amount when being applied to membrane cleaning, no generation of disinfection by-products, no secondary pollution and the like. Such as using H 2 O 2 The PVDF and PES membranes contaminated with Humic Acid (HA) -coupled iron manganese oxides were cleaned and found to contain 0.5% by weight of H 2 O 2 Cleaning for 5min can recover 97% or more of the membrane flux and remove almost all irreversible contamination due to hydroxyl radical (OH) generation · ). In addition, the enzymatic reaction is H with Glucose Oxidase (GOD) 2 O 2 Source of Fe 3 O 4 Chemical enzyme cascade reaction with nano-particles as catalyst and GOD-Fe 3 O 4 Formation of system, OH · Proved to be the main active substance for membrane flux recovery. Thus, these outstanding achievements in membrane cleaning performance are mainly attributed to OH · Is a nonselective reactive species with oxidation strength greater than that of the species aloneH of (A) 2 O 2 And is stronger.
In these systems, OH for effective membrane cleaning · Production of (2) requires the construction of a Fenton-like system involving metal oxides and due to OH · High reactivity to target compounds and organic/inorganic components competing in water, as well as self-quenching by radical chain reaction, may result in poor catalytic durability. At the same time, OH · Strong oxidation strength of ((E) 0 (OH · /H 2 O) = 1.9-2.7V) may pose a potential threat to membrane matrix materials during long term cleaning. Therefore, there is a need to explore a non-radical pathway for more efficient and longer lasting membrane cleaning.
Disclosure of Invention
The invention aims to solve the technical problems, and provides a peroxide composite sustained-release tablet, and a preparation method and application thereof.
The peroxide composite sustained-release tablet consists of 40 to 100 parts by weight of solid peroxide, 5 to 40 parts by weight of catalytic assistant, 1 to 50 parts by weight of solid weak acid, 1 to 30 parts by weight of lubricant, 1 to 40 parts by weight of water absorbing material and 1 to 20 parts by weight of Tetraacetylethylenediamine (TAED).
A preparation method of peroxide composite sustained-release tablets comprises the following steps:
the method comprises the following steps: weighing 40-100 parts of solid peroxide, 5-40 parts of catalytic assistant, 1-50 parts of solid weak acid, 1-30 parts of lubricant, 1-40 parts of water absorbing material and 1-20 parts of tetraacetylethylenediamine according to parts by weight;
step two: and (2) under a drying condition, uniformly mixing the solid peroxide, the catalytic assistant, the solid weak acid, the lubricant, the water absorbing material and the tetraacetylethylenediamine weighed in the step one, and tabletting to obtain the peroxide composite sustained-release tablet.
The application of the peroxide composite sustained-release tablet is used for cleaning an ultrafiltration membrane in situ, and the cleaning method comprises the following steps:
filtering humic acid solution with the concentration of 0.1-1000 mg/L by the ultrafiltration membrane for 2-100 h to obtain the ultrafiltration membrane attached with humic acid; and (3) immersing the ultrafiltration membrane attached with the humic acid into water, adding the solid peroxide composite slow-release tablet, circularly cleaning the ultrafiltration membrane attached with the humic acid for 3-30 min, and finishing the in-situ cleaning of the ultrafiltration membrane attached with the humic acid by the solid peroxide composite slow-release tablet.
The principle of the invention is as follows:
in the test of the present invention, effective membrane flux recovery was achieved within only 5min, but 3% wt H, if a small amount of peroxide was simply tabletted and placed on the membrane surface contaminated with humic acid 2 O 2 After 5min of cleaning, the membrane flux recovery was not significant. ESR test and quenching experiment prove that 1 O 2 Is the most important oxidant for removing irreversible pollutants in a peroxide system. In addition, the peroxide system can generate oxygen bubbles more rapidly under the action of the iron oxide and manganese dioxide catalytic promoter and 1 O 2 and OH. Further enhancing membrane flux. The invention firstly provides novel CaO 2 The peroxide composite sustained-release tablet is used as a feasible non-free radical way for effectively removing irreversible membrane pollution under the condition of not adding other catalysts, and is catalyzed by ferric oxide and manganese dioxide auxiliary agents or in-situ membrane pollutant FeO x +MnO x The activated Fenton-like reaction obtains better cleaning performance, and provides guidance for the design of a green membrane cleaning strategy.
Calcium peroxide (CaO) 2 ) Provides the possibility of effective membrane cleaning of non-radical paths as liquid H 2 O 2 One of the most common and safest alternatives, caO, in terms of removal of various organic contaminants 2 System ratio H 2 O 2 The system has better removal effect on organic pollutants at neutral pH. It is found that Ca 2+ As a most environmentally friendly catalyst, it can be used by promoting H 2 O 2 The disproportionation reaction of (2) to produce singlet oxygen 1 O 2 ). With OH · Compared with, based on 1 O 2 CaO of (2) 2 The system generally has mild oxidation-reduction capability (2.2V) and is rich in electrons for attackOrganic pollutants (such as humic acid) have better selectivity, and the risk of membrane damage can be reduced in the long term. And CaO 2 Released by decomposition 1 O 2 Is more stable than free radicals, can react with HA containing phenolic functional groups to form hydrogen peroxide ketone, and participates in the degradation of the aromatic humic acid. At the same time, the user can select the required time, 1 O 2 as non-free radical species, has strong resistance to impurities (such as inorganic anions and natural organic matters) in water, and improves CaO 2 The anti-interference performance and feasibility of the system on membrane cleaning.
The invention has the beneficial effects that:
(1) The peroxide composite slow-release system provides a non-free radical way for removing membrane pollutants and effectively cleaning the membrane for the first time. In addition, with H 2 O 2 Compared with the system, the humic acid treated by the peroxide composite sustained-release system has weaker hydrophobicity and weaker fluorescence intensity, so that the humic acid is easier to hydrolyze and is removed from the surface of the membrane. The solid peroxide composite sustained-release tablet is convenient to use, the membrane assembly does not need to be moved out of a membrane pool and put in a cleaning agent for soaking and cleaning, and the prepared tablet is directly put in the polluted membrane pool for in-situ cleaning and is easy to control; the peroxide tablet releases hydrogen peroxide immediately when meeting water, and simultaneously generates oxygen bubbles and singlet oxygen to promote the stripping and desorption of pollutants from the surface of the membrane.
Through active substance identification experiments, a non-free radical path of a peroxide composite slow-release system is a main reason for prominent membrane cleaning performance, the oxidation-reduction potential of the non-free radical singlet oxygen is lower than that of a hydroxyl radical, so that an ultrafiltration membrane filament can be prevented from being corroded by the free radical in a long-term cleaning process, and meanwhile, the stability of the singlet oxygen which is a non-free radical is higher than that of the hydroxyl radical and is not easily quenched by impurities (such as inorganic anions, organic matters and the like) in water in a membrane cleaning process, so that the stability and the anti-interference capability of the peroxide composite slow-release system are improved. Under the catalytic action of catalytic assistants such as metal oxides and the like, the generated hydroxyl radicals are used as a spectral free radical to further enhance the removal of membrane pollution. More importantly, the peroxide composite slow-release system can not generate secondary pollutants, so that a green and sustainable non-free radical cleaning strategy is provided for the ultrafiltration membrane polluted by natural macromolecular organic matters.
The oxidation-reduction potential generated by the decomposition of the solid peroxide composite sustained-release tablet is lower than that of singlet oxygen of hydroxyl free radicals, and the singlet oxygen can only remove humic acid on the surface of the membrane, but has small damage effect on the surface of the membrane.
The product of the invention is a solid tablet, which is liquid H 2 O 2 More stable, easier to transport, can be stored for a long time under the condition of ventilation and drying; simple production and cost effectiveness in practical application.
(2) And H 2 O 2 In contrast, the solid peroxide composite sustained release tablets of the present invention are effective over a wide pH range and the reaction product is generally environmentally friendly. The invention can directly carry out tabletting without granulating, and has the advantages of time saving, energy saving, simple process, capability of avoiding the contact with water to increase the stability of the tablet and the like.
The invention can obtain a peroxide composite sustained-release tablet, and a preparation method and application thereof.
Drawings
FIG. 1 is a graph showing the comparison of the membrane flux recovery rates of hydrogen peroxide (3 wt%) and solid calcium peroxide composite sustained-release tablets in example 1 after they were used for membrane cleaning, respectively, wherein A represents hydrogen peroxide (3 wt%), and B represents solid calcium peroxide composite sustained-release tablets;
FIG. 2 is a graph showing the irreversible contamination resistance removal efficiency of the composite sustained-release tablet of hydrogen peroxide (3 wt%) and solid calcium peroxide in example 1 after the respective use for cleaning the membrane;
FIG. 3 shows H in example 1 when 2, 6-Tetramethylpiperidine (TEMP) is used as a singlet oxygen scavenger and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) is used as a scavenger of hydroxyl radicals 2 O 2 EPR map of (A) represents H 2 O 2 + TEMP, B stands for H 2 O 2 +DMPO；
FIG. 4 shows the singlet oxygen trapping agent of example 1, 2, 6-Tetramethylpiperidine (TEMP), 5-dimethyl-1-pyrroline-N-oxideCaO in the case of a substance (DMPO) as a scavenger of hydroxyl radicals 2 EPR map of the composite sustained-release tablet, A represents CaO 2 Composite sustained-release tablet + TEMP, B represents CaO 2 Composite sustained release tablet + DMPO, \9679andrepresents singlet oxygen: (A), (B), (C) 1 O 2 ) Duct: (OH) represents a hydroxyl radical.
Detailed Description
The first embodiment is as follows: the peroxide composite sustained-release tablet comprises, by weight, 40-100 parts of solid peroxide, 5-40 parts of a catalytic assistant, 1-50 parts of a solid weak acid, 1-30 parts of a lubricant, 1-40 parts of a water absorbing material, and 1-20 parts of tetraacetylethylenediamine.
The second embodiment is as follows: the present embodiment differs from the present embodiment in that: the solid peroxide is one or more of peroxides of sodium, potassium, calcium and magnesium.
Other steps are the same as those in the first embodiment.
The third concrete implementation mode: the first or second differences from the present embodiment are as follows: the catalytic promoter is one or more of manganese salt, ferric salt, ferrous salt, copper salt and cobalt salt, oxides and sulfides of manganese, iron, copper and cobalt, iron minerals and manganese minerals, and sodium and potassium persulfate, permanganate, ferrate and nano zero-valent iron.
The iron mineral is magnetite, pyrite, hematite, limonite, goethite, lepidocrocite, siderite and active ilmenite; the manganese ore is pyrolusite, psilomelane, manganite, limonite, hausmannite or rhodochrosite.
The other steps are the same as those in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment and one of the first to third embodiments is as follows: the mass ratio of the solid peroxide to the catalytic promoter is (1-20): 1; the solid peroxide is calcium peroxide; the catalytic assistant is manganese dioxide or ferroferric oxide.
The other steps are the same as those in the first to third embodiments.
The fifth concrete implementation mode is as follows: the difference between this embodiment and the first to the fourth embodiments is: the solid weak acid is one or more of boric acid, citric acid, malic acid, tartaric acid, formic acid and ascorbic acid; the lubricant is a water-soluble lubricant or a water-insoluble lubricant; the water-soluble lubricant is one or more of polyethylene glycol 1500, polyethylene glycol 4000, polyethylene glycol 6000, sodium dodecyl sulfate, magnesium dodecyl sulfate, L-leucine, sodium benzoate, sodium oleate, sodium chloride, sodium acetate and boric acid; the water-insoluble lubricant is one or more of magnesium stearate, talcum powder, superfine silica gel powder, sucrose fatty acid ester and sodium stearyl fumarate; the water-absorbing material is one or more of anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, silica gel, silicon dioxide and high-molecular water-absorbing resin.
The other steps are the same as those in the first to fourth embodiments.
The sixth specific implementation mode: the preparation method of the peroxide composite sustained-release tablet comprises the following steps:
the method comprises the following steps: weighing 40-100 parts of solid peroxide, 5-40 parts of catalytic assistant, 1-50 parts of solid weak acid, 1-30 parts of lubricant, 1-40 parts of water absorbing material and 1-20 parts of tetraacetylethylenediamine according to parts by weight;
step two: and (2) under a drying condition, uniformly mixing the solid peroxide, the catalytic assistant, the solid weak acid, the lubricant, the water absorbing material and the tetraacetylethylenediamine weighed in the step one, and tabletting to obtain the peroxide composite sustained-release tablet.
In the embodiment, the solid weak acid has the function of improving the disintegration performance of the tablet, and is beneficial to rapid disintegration, release and the like of the tablet; the lubricant is used for improving the stability of the tablet, and is beneficial to the production, processing and the like of the tablet; the water absorbing material is used for assisting in absorbing water in the surrounding environment and providing reaction medium water for peroxide.
Tetraacetyl ethylene diamine (TAED) is an activator of peroxide, can effectively improve the disinfection and sterilization functions of the peroxide, and in aqueous solution, tetraethyl ethylene diamine (TAED)The Acyl Ethylenediamine (TAED) can react with hydrogen peroxide in situ to generate a green ecological bactericide-peracetic acid (PAA, CH) with strong bactericidal capacity 3 C(O)OOH、E 0 =1.81 eV), the bactericidal effect of the cleaning agent is enhanced (particularly in an alkaline environment).
The seventh embodiment: the sixth difference between the present embodiment and the specific embodiment is: the second step of medium pressing is carried out according to the following steps:
(1) Adjusting the weight of the tablet: firstly, installing a punch die and a punch head of a tablet press, keeping a lower punch parallel to a middle die and on a horizontal plane when the lower punch is at the highest position by an adjusting screw rod, then adjusting the weight of tablets when the lower punch is adjusted to the lowest position by shaking a handle, measuring the thickness and the quality of the tablets, and then adjusting until the final weight and the thickness of the tablets are determined;
(2) Pressure regulation: the pressure of the tablet press is adjusted by adjusting the upper punch screw until the hardness of the tablet meets the quality requirement when the tablet is pressed; the quality requirements are as follows: (1) the hardness is moderate; (2) the color is uniform, and the appearance is smooth and complete; (3) the content of various raw materials after tabletting is accurate, and the requirement of weight difference is met; (4) the requirement of the disintegration time limit of the tablet is met;
(3) Preparation of tablets: adding solid peroxide, a catalytic assistant, solid weak acid, a lubricant, a water absorbing material and tetraacetylethylenediamine into a die, scraping the surface, keeping the surface horizontal, shaking a handle, and manually tabletting to obtain the solid peroxide composite sustained-release tablet.
The other steps are the same as in the sixth embodiment.
The specific implementation mode is eight: the sixth or seventh embodiment is different from the first embodiment in that: the drying conditions are temperature 1-30 deg.C and humidity 1-25%.
The other steps are the same as those of the sixth or seventh embodiment.
The specific implementation method nine: the peroxide composite sustained-release tablet is used for cleaning an ultrafiltration membrane in situ, and the cleaning method comprises the following steps:
filtering humic acid solution with the concentration of 0.1-1000 mg/L by the ultrafiltration membrane for 2-100 h to obtain the ultrafiltration membrane attached with humic acid; and (3) immersing the ultrafiltration membrane attached with the humic acid into water, adding the solid peroxide composite sustained-release tablet, circularly cleaning the ultrafiltration membrane attached with the humic acid for 3-30 min, and finishing the in-situ cleaning of the ultrafiltration membrane attached with the humic acid by the solid peroxide composite sustained-release tablet.
The detailed implementation mode is ten: the ninth embodiment is different from the ninth embodiment in that: the ultrafiltration membrane is a polyethersulfone flat membrane, the average pore diameter of the membrane is 10-100KDa, and the pure water flux under 0.1MPa is 30-300 LMH.
The other steps are the same as in the ninth embodiment.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: a preparation method of a peroxide compound sustained-release tablet comprises the following steps:
the method comprises the following steps: respectively weighing 75mg of calcium peroxide, 25mg of manganese dioxide, 10mg of solid weak acid, 8mg of lubricant, 6mg of water absorbing material and 2mg of Tetraacetylethylenediamine (TAED);
step two: under the drying condition (the temperature is 20 ℃, and the humidity is below 25%), mixing the calcium peroxide, the solid weak acid, the lubricant, the water absorbing material and the Tetraacetylethylenediamine (TAED) weighed in the step one, and tabletting to obtain a calcium peroxide white tablet; and then, spreading manganese dioxide powder on the calcium peroxide white tablets for continuous tabletting, packaging by using a high-barrier plastic bag, and sealing and storing.
The solid weak acid is citric acid; the lubricant is a water-soluble lubricant or a water-insoluble lubricant; the lubricant is water-soluble lubricant polyethylene glycol 1500 or the non-water-soluble lubricant is talcum powder; the water absorbing material is silica gel.
And (3) analyzing the pollution condition of the membrane: the ultrafiltration membrane in the laboratory is a Polyethersulfone (PES) flat membrane, and the average pore diameter of the membrane is 30KDa. The pure water flux under 0.1MPa is 65LMH, and the total membrane filtration area in the experiment is 32.15cm; after 6mg/L of humic acid solution for 6 hours: (1) the transmembrane pressure difference (TMP) of the ultrafiltration membrane rapidly increases in a short time. The pollutants gradually block the membrane pores to form a filter cake layer; (2) transmembrane pressure difference of the ultrafiltration membrane cannot be ideally recovered after daily maintainability deionized water cleaning; (3) the membrane flux is continuously reduced, and the water passing amount is seriously influenced.
The ultrafiltration membrane in the ultrafiltration cup is observed by naked eyes, a layer of dark brown sticky dirt appears on the surface of the membrane, the appearance is similar to that of mud dirt, after the membrane is washed by deionized water, the mud dirt cake layer on the surface is reduced, the dark brown color is changed into light brown color, and the flux of the tested membrane is unchanged.
The following cleaning protocol was adopted: (1) Firstly, the reaction condition of the solid peroxide composite sustained-release tablet is researched, and the test result shows that: (1) the tablet reacts immediately after contacting with water, and a large amount of oxygen microbubbles are generated on the surface and around the tablet, so that the dirt on the surface of the membrane is further desorbed; along with the time, the tablets are decomposed, the generation amount of micro bubbles is further increased, and then the tablets are pushed to move on the surface of the film and are further decomposed into small tablets, so that the bubbles are released more quickly; after reaching the reaction peak value, gradually entering a stage of slowly releasing oxygen for a long time, and realizing the continuous membrane cleaning effect of the solid peroxide composite sustained-release tablet; (2) the optimal reaction concentration of the solid calcium peroxide is 20-150mg/L, the reaction concentration of the manganese dioxide is 5-50mg/L, and the mass ratio of the calcium peroxide to the manganese dioxide is (2-5): 1.
(2) FIG. 1 is a graph showing the comparison of the membrane flux recovery rates of the solid calcium peroxide composite sustained-release tablet with hydrogen peroxide (3 wt%) in example 1 after the hydrogen peroxide (3 wt%) is used for cleaning the membrane, and B represents the solid calcium peroxide composite sustained-release tablet. As shown in figure 1, the solid calcium peroxide composite sustained-release tablet prepared by tabletting calcium peroxide and manganese dioxide with the optimal mass ratio is used for membrane cleaning, and simultaneously 3wt% of liquid H is mixed with common oxidation cleaning agent in the cleaning process 2 O 2 Comparing the flux recovery of the ultrafiltration membrane, and using oxidation cleaning agent H 2 O 2 (3 wt%) after 5 minutes of washing, the membrane flux was only restored from 52% to 58% with a removal rate of only 22% for irreversible fouling. And after the solid calcium peroxide composite sustained-release tablet is cleaned for 5 minutes, the membrane flux can be recovered from 52 percent to 98 percent, and the irreversible membrane pollution of 97 percent is removed. As can be seen, after the ultrafiltration membrane is cleaned in situ by adopting the membrane cleaning scheme of the solid peroxide composite sustained-release tablet in the embodiment, pollutants are generated after the ultrafiltration membrane is cleaned in situThe membrane flux is substantially recovered and increased, the original flux level of a clean membrane is substantially reached, and the membrane structure is not damaged by long-time cleaning.
Fig. 2 is a graph comparing the irreversible contamination resistance removal efficiency of the hydrogen peroxide (3 wt%) and the solid calcium peroxide composite sustained-release tablet of example 1 after being used for cleaning the membrane, respectively, and experimental conditions: transmembrane pressure difference is 0.1MPa; initial concentration of humic acid: 6mg/L. As shown in fig. 2, the removal efficiency of the irreversible contamination resistance after the hydrogen peroxide (3 wt%) is used for cleaning the membrane is only about 20%, while the removal efficiency of the irreversible contamination resistance after the solid calcium peroxide composite sustained-release tablet is used for cleaning the membrane is as high as more than 95%, and the difference of the removal efficiency is obvious.
Table 1 shows the hydrogen peroxide content variation;
TABLE 1
As shown in Table 1, in the present embodiment, calcium peroxide not only can prolong the release time of hydrogen peroxide and slow down the decay of hydrogen peroxide concentration, but also can continuously clean the contaminated membrane surface, and the overall effect is much higher than that of H 2 O 2 。
FIG. 3 shows H in example 1 when 2, 6-Tetramethylpiperidine (TEMP) is used as a singlet oxygen scavenger and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) is used as a scavenger of hydroxyl radicals 2 O 2 EPR map of (A) represents H 2 O 2 + TEMP, B stands for H 2 O 2 + DMPO; FIG. 4 shows CaO in the case of example 1 in which 2, 6-Tetramethylpiperidine (TEMP) is used as a singlet oxygen scavenger and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) is used as a hydroxyl radical scavenger 2 EPR map of the composite sustained-release tablet, A represents CaO 2 Composite sustained release tablet + TEMP, B represents CaO 2 Composite slow-release tablet + DMPO' \9679andsingle-state oxygen (C) ((C)) 1 O 2 ) Duct: (OH) represents a hydroxyl radical.
To verify CaO 2 Composite sustained releaseElectron paramagnetic resonance (ESR) test experiments were performed on active oxygen species in tablets that contributed to the membrane cleaning process using 2, 6-Tetramethylpiperidine (TEMP) as a scavenger of singlet oxygen and 5, 5-dimethyl-1-pyrroline-N-oxide (DMPO) as a scavenger of hydroxyl radicals. After capture of TEMP and DMPO, H is shown in FIGS. 3-4 2 O 2 No obvious signal is generated; and CaO 2 The composite sustained-release tablet generates singlet oxygen with selective removal effect on humic acid pollutants rich in electrons and hydroxyl free radicals with broad-spectrum pollutant removal property in the membrane cleaning process.
Claims (10)
1. The peroxide composite sustained-release tablet is characterized by consisting of 40-100 parts by weight of solid peroxide, 5-40 parts by weight of catalytic assistant, 1-50 parts by weight of solid weak acid, 1-30 parts by weight of lubricant, 1-40 parts by weight of water absorbing material and 1-20 parts by weight of tetraacetylethylenediamine.
2. The peroxide composite sustained-release tablet according to claim 1, wherein the solid peroxide is one or more of peroxides of sodium, potassium, calcium and magnesium.
3. The peroxide composite sustained-release tablet according to claim 1, wherein the catalytic promoter is one or more of manganese salt, ferric salt, ferrous salt, copper salt and cobalt salt, oxides, sulfides, iron minerals and manganese minerals of manganese, iron, copper and cobalt, and persulfate, permanganate, ferrate and nano zero-valent iron of sodium and potassium.
4. The peroxide composite sustained-release tablet according to claim 1, 2 or 3, wherein the mass ratio of the solid peroxide to the catalytic assistant is (1-20): 1; the solid peroxide is calcium peroxide; the catalytic assistant is manganese dioxide or ferroferric oxide.
5. The peroxide composite sustained-release tablet according to claim 1, wherein the solid weak acid is one or more of boric acid, citric acid, malic acid, tartaric acid, formic acid and ascorbic acid; the lubricant is a water-soluble lubricant or a water-insoluble lubricant; the water-soluble lubricant is one or more of polyethylene glycol 1500, polyethylene glycol 4000, polyethylene glycol 6000, sodium dodecyl sulfate, magnesium dodecyl sulfate, L-leucine, sodium benzoate, sodium oleate, sodium chloride, sodium acetate and boric acid; the water-insoluble lubricant is one or more of magnesium stearate, talcum powder, superfine silica gel powder, sucrose fatty acid ester and sodium stearyl fumarate; the water absorbing material is one or more of anhydrous calcium chloride, anhydrous magnesium sulfate, anhydrous magnesium chloride, silica gel, silicon dioxide and high-molecular water absorbing resin.
6. The process for preparing a peroxide composite sustained-release tablet according to any one of claims 1 to 5, which comprises the steps of:
the method comprises the following steps: weighing 40-100 parts of solid peroxide, 5-40 parts of catalytic promoter, 1-50 parts of solid weak acid, 1-30 parts of lubricant, 1-40 parts of water absorbing material and 1-20 parts of tetraacetylethylenediamine according to parts by weight;
step two: and (2) under a drying condition, uniformly mixing the solid peroxide, the catalytic assistant, the solid weak acid, the lubricant, the water absorbing material and the tetraacetylethylenediamine weighed in the step one, and tabletting to obtain the peroxide composite sustained-release tablet.
7. The method for preparing the peroxide compound sustained-release tablet according to claim 6, wherein the second intermediate-pressure tablet is prepared by the following steps:
(1) Adjusting the weight of the tablet: firstly, mounting a punch die and a punch head of a tablet press, keeping a lower punch parallel to a middle die and on a horizontal plane when the lower punch is at the highest position by an adjusting screw rod, then, rocking a handle to adjust the weight of tablets when the lower punch is adjusted to the lowest position, measuring the thickness and the quality of the tablets, and then, adjusting until the final weight and the final thickness of the tablets are determined;
(2) Pressure regulation: the pressure of the tablet press is adjusted by adjusting the upper punch screw until the hardness of the tablet meets the quality requirement when the tablet is pressed; the quality requirement is as follows: (1) the hardness is moderate; (2) the color is uniform, and the appearance is smooth and complete; (3) the content of each raw material after tabletting is accurate, and the requirement of weight difference is met; (4) the requirement of the disintegration time limit of the tablet is met;
(3) Preparation of tablets: adding solid peroxide, a catalytic assistant, solid weak acid, a lubricant, a water absorbing material and tetraacetylethylenediamine into a die, scraping the surface, keeping the surface horizontal, shaking a handle, and manually tabletting to obtain the solid peroxide composite sustained-release tablet.
8. The method for preparing a peroxide composite sustained-release tablet according to claim 6, wherein the drying conditions are a temperature of 1-30 ℃ and a humidity of 1-25%.
9. The use of a peroxide composite sustained-release tablet according to claim 1, wherein the peroxide composite sustained-release tablet is used for cleaning an ultrafiltration membrane in situ, and the cleaning method comprises the following steps:
filtering humic acid solution with the concentration of 0.1-1000 mg/L by the ultrafiltration membrane for 2-100 h to obtain the ultrafiltration membrane attached with humic acid; and (3) immersing the ultrafiltration membrane attached with the humic acid into water, adding the solid peroxide composite sustained-release tablet, circularly cleaning the ultrafiltration membrane attached with the humic acid for 3-30 min, and finishing the in-situ cleaning of the ultrafiltration membrane attached with the humic acid by the solid peroxide composite sustained-release tablet.
10. The use of the peroxide composite sustained-release tablet according to claim 9, wherein the ultrafiltration membrane is a polyethersulfone flat membrane, the average pore diameter of the membrane is 10-100KDa, and the pure water flux under 0.1MPa is 30-300 LMH.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275943A (en) * | 1991-04-12 | 1994-01-04 | Dituro John W | Timed-release tablets for biological degradation of organic matter |
| US20070056904A1 (en) * | 2003-07-04 | 2007-03-15 | Hogt Andreas H | Cleaning of filtration membranes with peroxides |
| US20170321184A1 (en) * | 2016-05-09 | 2017-11-09 | Global Algae Innovations, Inc. | Biological and algae harvesting and cultivation systems and methods |
| US20190071621A1 (en) * | 2013-11-11 | 2019-03-07 | Whiteley Corporation Pty. Ltd. | Process for removal of biofilm |
-
2022
- 2022-11-24 CN CN202211485922.7A patent/CN115770487A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5275943A (en) * | 1991-04-12 | 1994-01-04 | Dituro John W | Timed-release tablets for biological degradation of organic matter |
| US20070056904A1 (en) * | 2003-07-04 | 2007-03-15 | Hogt Andreas H | Cleaning of filtration membranes with peroxides |
| US20190071621A1 (en) * | 2013-11-11 | 2019-03-07 | Whiteley Corporation Pty. Ltd. | Process for removal of biofilm |
| US20170321184A1 (en) * | 2016-05-09 | 2017-11-09 | Global Algae Innovations, Inc. | Biological and algae harvesting and cultivation systems and methods |
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