step S22, under the condition of nitrogen protection, mixing methanol and the intermediate 1, heating, refluxing and stirring, adding epoxy chloropropane while stirring, keeping the temperature unchanged after the addition, continuing to react for 2 hours, cooling to room temperature after the reaction is finished, reducing the temperature, concentrating under reduced pressure to remove the solvent, eluting with anhydrous ether for three times, and then drying in vacuum for 24 hours at 40 ℃ to obtain the auxiliary agent; wherein the dosage ratio of the methanol to the intermediate 1 to the epichlorohydrin is 10 mL: 3 g: 1g of the total weight of the composition.

The reaction process is as follows:

the modified activated carbon is prepared by the following steps:

step A11, placing the activated carbon in a muffle furnace, heating for 30min at the temperature of 300 ℃, then washing with distilled water until the washing liquid has no obvious black color, and drying at the temperature of 40 ℃ to constant weight after washing to obtain solid powder;

step A22, mixing the zinc-copper mixed solution and the sodium tartrate solution, adding deionized water to prepare electrolyte, adjusting the pH value of the electrolyte to 13 by using 1mol/L sodium hydroxide solution, uniformly spreading the solid powder prepared in the step A11 on a stainless steel net, electrolyzing for 3min by using 12V direct current, taking out the solid powder after the electrolysis is finished, washing for three times by using distilled water, and drying for 30min at the temperature of 300 ℃ to obtain modified activated carbon; wherein the molar ratio of zinc to copper in the zinc-copper mixed solution is 1: 1, wherein the concentration of copper is 30 g/L; the concentration of the sodium tartrate solution is 150 g/L; the volume ratio of the zinc-copper mixed solution to the sodium tartrate solution to the deionized water is 1: 1: 3.

a production process of a high-efficiency purification material for a floating liquid in a space capsule comprises the following steps:

firstly, weighing polyaluminum ferric chloride, polyacrylamide, bentonite, calcium lignosulfonate, basic aluminum chloride and modified filler in parts by weight, uniformly mixing the materials by adopting a wet ball milling method, heating the mixture to 170 ℃ under a vacuum condition, adding polyethylene glycol 400, carrying out spray granulation, and carrying out compression molding;

and secondly, preserving the heat for 2-3 hours at the temperature of 500-550 ℃ in a nitrogen atmosphere to obtain the high-efficiency purifying material for the floating liquid in the space capsule.

The invention has the beneficial effects that:

the floating liquid is treated by sequentially carrying out multiple filtration treatment on PP cotton, granular activated carbon UDF and the efficient purification material prepared in the invention, wherein the PP cotton is used for filtering to remove large particles such as rust, sand and stone and impurities, and filtering the granules in the floating liquid to 1 micron, and the granular activated carbon UDF has a porous structure, integrates adsorption, filtration, interception and catalysis, can effectively remove organic matters and other radioactive substances in the floating liquid, has the effects of decoloring and deodorizing, and is combined with the efficient purification material prepared in the invention to carry out a more comprehensive purification process.

The raw materials of the high-efficiency purification material contain modified filler; the modified filler is prepared by swelling modified chitosan under acidic condition to make unreacted-NH on the modified chitosan₂to-NH₃⁺Adding modified active carbon for compounding, adding glutaraldehyde for crosslinking to obtain a solution a, then adding thiosemicarbazide, and reacting the thiosemicarbazide with aldehyde groups on the crosslinked glutaraldehyde to obtain the modified fillerAnd (5) feeding. In the process of preparing the modified chitosan, amino groups of the chitosan react with aldehyde groups of vanillin to generate a solid b containing a Schiff base structure, the solid b contains a hydroxyl structure on the vanillin, so that the solid b reacts with epoxy groups on the auxiliary agent, and the auxiliary agent containing a quaternary ammonium salt structure is introduced; the modified chitosan contains Schiff base structure with corrosion inhibition effect, so that the modified filler has certain corrosion inhibition effect, the corrosion of the high-efficiency purification material prepared by the method to a metal carrier or a metal filter in the purification process is reduced, the quaternary ammonium salt structure is introduced into the modified chitosan, so that the modified chitosan contains long-chain alkyl and quaternary ammonium salt structure, wherein the quaternary ammonium salt structure can perform cationization reaction with oxygen-containing groups on the surface of the modified activated carbon, the quaternary ammonium salt groups are prevented from falling off in the purification process, the antibacterial property of the modified filler is improved, the high-efficiency purification material added with the modified filler has a sterilization effect in the purification process, and the cleanliness of the floating liquid is improved. The modified activated carbon is prepared by taking activated carbon as a carrier, loading copper-zinc metal on the activated carbon by an electrodeposition method, and removing residual chlorine in water; the modified filler added with the modified activated carbon improves the removal rate of the residual chlorine by the purification material.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

Preparing an auxiliary agent:

step S21, mixing lauric acid and xylene, heating to dissolve, then dropwise adding diethylenetriamine, heating to 140 ℃ until water is generated, heating to 240 ℃ at the speed of 5 ℃/min until no water is separated, after the reaction is finished, cooling to 120 ℃, decompressing and concentrating to remove the solvent, and then recrystallizing with acetone to obtain an intermediate 1;

and step S22, under the condition of nitrogen protection, mixing methanol and the intermediate 1, heating, refluxing and stirring, adding epoxy chloropropane while stirring, keeping the temperature unchanged after the addition, continuing to react for 2 hours, cooling to room temperature after the reaction is finished, reducing the temperature to remove the solvent by concentration under reduced pressure, eluting for three times by using anhydrous ether, and then drying for 24 hours in vacuum at 40 ℃ to obtain the auxiliary agent.

Wherein, the dosage ratio of the lauric acid, the xylene and the diethylenetriamine in the step S21 is 0.1 mol: 30mL of: 0.11 mol; in the step S22, the using amount ratio of the methanol to the intermediate 1 to the epichlorohydrin is 10 mL: 3 g: 1g of the total weight of the composition.

Example 2

Preparing modified activated carbon:

example 3

Preparing modified chitosan:

step S11, mixing chitosan and methanol, stirring and mixing for 6h at the temperature of 25 ℃, then dropwise adding a methanol solution of vanillin, heating to 65 ℃ after dropwise adding, stirring and reacting for 12h, filtering after the reaction is finished, washing the obtained filter cake with methanol, and drying at 40 ℃ to constant weight after washing is finished to obtain a solid b;

and step S12, mixing the solid b and an auxiliary agent, adding isopropanol, adding a sodium hydroxide solution while stirring, carrying out reflux reaction for 24 hours at the temperature of 70 ℃, carrying out vacuum filtration after the reaction is finished, washing a filter cake with the isopropanol, and drying at the temperature of 40 ℃ to constant weight to obtain the modified chitosan.

Wherein the methanol solution of vanillin in the step S11 is prepared by mixing vanillin and methanol according to the ratio of 9 g: 40mL of the mixture is mixed; the dosage ratio of the chitosan to the methanol to the vanillin is 3 g: 200mL of: 40 mL; in the step S12, the concentration of the sodium hydroxide solution is 2mol/L, and the dosage ratio of the solid b, the auxiliary agent, the isopropanol and the sodium hydroxide solution is 2 g: 6 g: 100mL of: 0.5 mL; the adjuvant was prepared as in example 1.

Example 4

The modified filler is prepared by the following steps:

firstly, mixing modified chitosan and acetic acid solution with the mass fraction of 5%, reacting for 7 hours at the temperature of 70 ℃, adding modified activated carbon, keeping the temperature unchanged, continuing stirring for 20 minutes, adding glutaraldehyde with the mass fraction of 5%, stirring and reacting for 6 hours at the temperature of 70 ℃ after the addition is finished, obtaining mixed solution a, and dropwise adding sodium hydroxide solution with the volume fraction of 5% in the reaction process to control the pH value of the reaction solution to be 9;

and secondly, adding thiosemicarbazide into the mixed solution a, heating and stirring for 4 hours at the temperature of 70 ℃, decompressing and filtering after the reaction is finished, washing a filter cake with ethanol and distilled water in sequence, and drying to constant weight at the temperature of 60 ℃ after the washing is finished to obtain the modified filler.

Wherein the dosage ratio of the modified chitosan, the acetic acid solution with the mass fraction of 5 percent, the modified activated carbon and the glutaraldehyde with the mass fraction of 5 percent is 8 g: 60mL of: 3 g: 60 mL; the dosage ratio of the mixed solution a to the thiosemicarbazide is 135 mL: 4g of the total weight of the mixture; modified activated carbon was prepared as in example 2; the modified chitosan was prepared as in example 3.

Example 5

and secondly, preserving the heat for 2 hours at 500 ℃ in a nitrogen atmosphere to obtain the high-efficiency purifying material for the floating liquid in the space capsule.

Wherein, the weight parts of the substances are 75 parts of polyaluminum ferric chloride, 55 parts of polyacrylamide, 10 parts of bentonite, 5 parts of calcium lignosulfonate, 6 parts of basic aluminum chloride, 6 parts of polyethylene glycol 4006 and 10 parts of modified filler; the modified filler was prepared as in example 4.

Example 6

and secondly, preserving the heat for 2.5 hours at 525 ℃ in a nitrogen atmosphere to obtain the high-efficiency purifying material for the floating liquid in the space capsule.

Wherein the weight parts of the components are 80 parts of polyaluminum ferric chloride, 60 parts of polyacrylamide, 15 parts of bentonite, 10 parts of calcium lignosulfonate, 8 parts of basic aluminum chloride, 4006.5 parts of polyethylene glycol and 15 parts of modified filler; the modified filler was prepared as in example 4.

Example 7

and secondly, preserving the heat for 3 hours at 550 ℃ in a nitrogen atmosphere to obtain the high-efficiency purifying material for the floating liquid of the space capsule.

Wherein the weight parts of the components are 90 parts of polyaluminum ferric chloride, 65 parts of polyacrylamide, 20 parts of bentonite, 15 parts of calcium lignosulfonate, 10 parts of basic aluminum chloride, 7 parts of polyethylene glycol 4007 and 20 parts of modified filler; the modified filler was prepared as in example 4.

Comparative example 1

The modified chitosan in example 4 was replaced with unmodified chitosan, and the remaining raw materials and preparation process remained the same.

Comparative example 2

The modified activated carbon from example 4 was replaced by unmodified activated carbon, and the remaining raw materials and preparation process were kept unchanged.

Comparative example 3

The modified filler of example 8 was not added, and the remaining raw materials and preparation process remained unchanged.

Comparative example 4

The modified filler of example 8 was replaced with the sample prepared in comparative example 1, and the remaining raw materials and preparation process were maintained.

Comparative example 5

The modified filler of example 8 was replaced with the sample prepared in comparative example 2, and the remaining raw materials and preparation process were maintained.

The samples obtained in examples 5 to 7 and comparative examples 3 to 5 were tested at a feed water residual chlorine concentration of 0.6 mg/L; the samples prepared in examples 5 to 7 and comparative examples 3 to 5 were tested for residual chlorine in the effluent after purification at a feed rate of 36L/h;

taking the initial bacterial liquid with the concentration of 10⁵And (3) carrying out sterilization detection on the CFU/mL water sample, determining the sterilization rate of the water sample, and calculating the sterilization rate by using a flat plate counting method, wherein the specific method refers to GB 4789.2-94.

The test results are shown in table 1 below.

TABLE 1

Item	Example 5	Example 6	Example 7	Comparative example 3	Comparative example 4	Comparative example 5
							Residual chlorine in effluent/(mg/L)	0.15	0.14	0.15	0.35	0.18	0.30
Sterilization rate/(%)	98.7	98.9	98.9	65.3	83.6	93.8

From the above table 1, it can be seen that the purification material prepared by the present invention has high removal rate of residual chlorine and excellent sterilization effect.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The high-efficiency purification material for the floating liquid in the space capsule is characterized by comprising the following raw materials in parts by weight:

the modified filler is prepared by the following steps:

firstly, mixing modified chitosan and acetic acid solution with the mass fraction of 5%, reacting for 7 hours at the temperature of 70 ℃, adding modified activated carbon, keeping the temperature unchanged, continuing stirring for 20 minutes, adding glutaraldehyde with the mass fraction of 5%, and stirring for reacting for 4-7 hours at the temperature of 70 ℃ after the addition is finished to obtain mixed solution a;

and secondly, adding thiosemicarbazide into the mixed solution a, and heating and stirring for 4 hours at the temperature of 70 ℃ to obtain the modified filler.

2. The high-efficiency purification material for the floating liquid in the space capsule as claimed in claim 1, wherein the dosage ratio of the modified chitosan, the 5% by mass of acetic acid solution, the modified activated carbon and the 5% by mass of glutaraldehyde is 8 g: 60mL of: 3 g: 60 mL; the dosage ratio of the mixed solution a to the thiosemicarbazide is 135 mL: 4g of the total weight.

3. The high-efficiency purification material for the floating liquid in the space capsule as claimed in claim 1, wherein the modified chitosan is prepared by the following steps:

step S11, mixing chitosan and methanol, stirring and mixing for 6h at the temperature of 25 ℃, then dropwise adding a methanol solution of vanillin, heating to 65 ℃ after dropwise adding, and stirring and reacting for 12h to obtain a solid b;

and step S12, mixing the solid b and an auxiliary agent, adding isopropanol, adding a sodium hydroxide solution while stirring, and carrying out reflux reaction for 24 hours at the temperature of 70 ℃ to obtain the modified chitosan.

4. The efficient purifying material for floating liquid in space capsule as claimed in claim 3, wherein the methanol solution of vanillin in step S11 is vanillin and methanol in a dosage ratio of 9 g: 40mL of the mixture is mixed; the dosage ratio of the chitosan to the methanol to the vanillin is 3 g: 200mL of: 40 mL; in the step S12, the concentration of the sodium hydroxide solution is 2mol/L, and the dosage ratio of the solid b, the auxiliary agent, the isopropanol and the sodium hydroxide solution is 2 g: 6 g: 100mL of: 0.5 mL.

5. A high efficiency purification material for floating liquid in space capsule as claimed in claim 3, wherein the auxiliary agent is prepared by the following steps:

step S21, mixing lauric acid and xylene, heating to dissolve, then dropwise adding diethylenetriamine, heating to 140 ℃ until water is generated, heating to 240 ℃ at a speed of 5 ℃/min, and reacting until no water is generated, so as to obtain an intermediate 1;

and step S22, under the protection of nitrogen, mixing methanol and the intermediate 1, heating, refluxing and stirring, adding epoxy chloropropane while stirring, keeping the temperature unchanged after the addition, and continuing to react for 2 hours to obtain the auxiliary agent.

6. The high-efficiency purifying material for the floating liquid in the space capsule as claimed in claim 5, wherein the ratio of the amount of the lauric acid, the xylene and the diethylenetriamine in the step S21 is 0.1 mol: 30mL of: 0.11 mol; in the step S22, the using amount ratio of the methanol to the intermediate 1 to the epichlorohydrin is 10 mL: 3 g: 1g of the total weight of the composition.

7. The process for producing a high efficiency purifying material for floating liquid in space capsule as claimed in claim 1, comprising the steps of: