CN109987586B - Method for adsorbing hydrogen peroxide generated by photolysis of water system - Google Patents
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Abstract
The invention discloses a method for adsorbing hydrogen peroxide generated by a photolysis water system, wherein the photolysis water system comprises water, a photolysis catalyst, a light source and a stirrer, the water is subjected to photolysis under the irradiation condition of the light source and the catalytic action of the photolysis catalyst to generate hydrogen peroxide, an adsorbing material for adsorbing the hydrogen peroxide is arranged on the outer side of the photolysis water system, the adsorbing material and the photolysis water system are arranged in the same container, and the adsorbing material and the photolysis water system are separated by a filter membrane. The method can stably adsorb and enrich hydrogen peroxide in the process of photolyzing water.
Description
Technical Field
The invention relates to the technical field of photolytic water and hydrogen peroxide, in particular to a method for adsorbing hydrogen peroxide generated by a photolytic water system.
Background
The English name of Hydrogen Peroxide is Hydrogen Peroxide, and the chemical formula is H2O2The water-soluble organic acid can be mixed with water in any proportion, and the mixed water solution is colorless transparent liquid, commonly called as hydrogen peroxide. Peroxide [ -O-]2-The oxygen in the hydrogen peroxide shows a valence of-1, so that electrons can be easily obtained and reduced to a valence of-2, and the electrons can be lost and increased to a valence of 0, so that the hydrogen peroxide has very active chemical properties, and has strong oxidizing property and weak reducing property. Whether oxidizing or reducing, the final product H of the reaction is participated by hydrogen peroxide2O and O2All are natural substances, and do not cause secondary pollution to the environment, so the method is widely applied in the chemical field. However, hydrogen peroxide is unstable and gradually decomposes into H at room temperature2O and O2And if heated or exposed to light, the material decomposes more quickly and is easily destroyed, so that the material is usually required to be protected from light.
The prior art methods for producing hydrogen peroxide include electrolysis, isopropanol oxidation, oxygen cathode reduction, direct hydrogen-oxygen synthesis, and anthraquinone processes. The anthraquinone process is mature and becomes the main method for producing hydrogen peroxide in the world at present. However, the above production processes all require large and complicated production equipment, such as an electrolytic cell and a reaction tower, and in order to increase the concentration and purity of hydrogen peroxide, the reaction product needs to be separated for many times by a complicated extraction device to obtain relatively pure hydrogen peroxide.
Photolysis of water also produces hydrogen peroxide, and reports on TiO in Chem.Rev.1995,95: 735-7602As a photocatalyst, ■ OH free radicals are generated in the water system by photolysis at 300K, and then hydrogen peroxide is generated by coupling, namely ■ OH + ■ OH → H2O2However, because the main substance in the photolytic water system is water, the concentration of hydrogen peroxide is very low, and hydrogen peroxide can be decomposed quickly in the photolytic process, the prior art has no possibility of utilizing hydrogen peroxide basically in the photolytic water system, and utilizes the oxidation performance of ■ OH free radicals or O generated by decomposing water and hydrogen peroxide more2And H2To be utilized. In conclusion, the amount of hydrogen peroxide in the photolysis water system is small, and the hydrogen peroxide is easy to decompose, so that the hydrogen peroxide in the photolysis water system cannot be adsorbed and utilized without consideration in the prior art.
Those skilled in the chemical arts are familiar with two distinct roles, adsorption and catalysis, where adsorption is achieved by selectively accumulating one or more components of a fluid with a porous solid material having a large surface area, called adsorbent (adsorbate), to separate the components of a mixture; the catalysis is to change the activation energy of reactants through a catalyst (catalyst) so as to change the chemical reaction rate, and the quality and chemical properties of the catalyst before and after the reaction are kept unchanged. For hydrogen peroxide, in the prior art, other impurities are usually adsorbed for purifying hydrogen peroxide, for example, in CN107556426A, fluorine-containing acrylic resin is used to adsorb organic impurities and inorganic salt impurities in hydrogen peroxide products. Hydrogen peroxide can be decomposed in photolytic water system to generate hydroxyl radical, which can generate strong oxidation, for example, CN107522256A specification [0009 ]]The catalyst disclosed in the paragraph is adsorption with adsorption propertiesThe composition of carrier and photocatalyst with photocatalytic performance includes active carbon or molecular sieve as adsorbent and TiO as photocatalyst2Or supporting TiO2The hydrogen peroxide is added to improve the photodegradation efficiency, and the adsorbent carrier, the photocatalyst and the hydrogen peroxide are used for degrading organic pollutants in the sewage and purifying the water. Therefore, the prior art relating to adsorption and catalysis of hydrogen peroxide has the starting point of removing impurities except hydrogen peroxide, which is undoubtedly a great deal of work and cannot remove all impurities completely.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art: the method for adsorbing hydrogen peroxide generated by a photolytic water system is provided, and hydrogen peroxide can be stably adsorbed and enriched in the photolytic water process.
The technical solution of the invention is as follows: the utility model provides a method of hydrogen peroxide solution that absorption is generated by water system of photodissociation, water system of photodissociation includes water, photolysis catalyst, light source and agitator, and water takes place the photolysis under the irradiation condition of light source and the catalytic action of photolysis catalyst, generates hydrogen peroxide solution, is equipped with the adsorption material that is used for adsorbing hydrogen peroxide solution in the water system of photodissociation outside, and the adsorption material is placed in same container with the water system of photodissociation and is separated through the filter membrane between the two.
The specific operation process of the method is as follows:
1) separating the container by a filter membrane into two parts, wherein one part is a photolysis water system, and the other part is added with an adsorption material for adsorbing hydrogen peroxide;
2) starting a light source and a stirrer, so that water is subjected to photolysis under the irradiation condition of the light source and the catalytic action of a photolysis catalyst to generate hydrogen peroxide;
3) and (3) allowing the hydrogen peroxide to penetrate through the filter membrane and be adsorbed on the adsorbing material, taking out the adsorbing material adsorbed with the hydrogen peroxide after the adsorbing material adsorbs a predetermined amount of hydrogen peroxide, and separating the hydrogen peroxide.
Compared with the prior art, the method for adsorbing hydrogen peroxide generated by photolyzing a water system has the following remarkable advantages and beneficial effects:
the adsorption material has the function of adsorbing hydrogen peroxide generated in a photolysis water system, the specific mechanism is that ■ OH free radicals are generated by water photolysis and then coupled to generate hydrogen peroxide, although the hydrogen peroxide generated in the photolysis water system has a small amount and low concentration, the hydrogen peroxide can pass through a filter membrane in water and be adsorbed onto a solid adsorption material, and the hydrogen peroxide is stably attached to the surface of the adsorption material. Moreover, the photolysis catalyst and the adsorption material are both solid materials and are respectively positioned on two sides of the filter membrane, so that the photolysis catalyst and the adsorption material can block light rays from irradiating hydrogen peroxide, and the decomposition of the hydrogen peroxide is obviously reduced. In conclusion, the adsorption material can stably adsorb and enrich generated hydrogen peroxide in the water photolysis process, and the efficiency of the water photolysis reaction is improved.
Compared with the existing hydrogen peroxide production technology, the method does not need large and complex production equipment such as an electrolytic cell, a reaction tower and the like, only needs a simple container, separates the container into two parts which are used for accommodating the adsorption material and the photolysis water system respectively by using a filter membrane, and then starts a light source and a stirrer, so that the adsorption material can be adsorbed in the photolysis water process to obtain the hydrogen peroxide with higher concentration and purity. Compared with the existing water photolysis technology, the method creatively adsorbs and collects hydrogen peroxide generated in the water photolysis process, so that a small amount of hydrogen peroxide is concentrated on the adsorption material and stably attached to the adsorption material, and is not easily decomposed, and the hydrogen peroxide is really recycled.
The technology of the invention fills the blank of utilizing the photolysis technology in the field of hydrogen peroxide, adsorbs and enriches hydrogen peroxide which cannot be utilized by a photolysis system in the industry, and has good application prospects in the aspects of hydrogen peroxide recovery, green oxidation, photocatalysis technology and the like.
Because adsorption material itself does not have the effect of photolysis catalysis, if not keep apart with the photolysis water system, adsorption material can hinder the catalytic action of photolysis catalyst, can make absorbent hydrogen peroxide solution decompose very fast under the illumination after adsorbing moreover, consequently need separate adsorption material and photolysis water system through the filter membrane, guarantees that the reaction of photolysis water is normally effectively gone on, improves adsorption efficiency.
Preferably, the adsorption material is a titanium-silicon molecular sieve with a Si-O-Ti bond framework structure, a vanadium-silicon molecular sieve with a Si-O-V bond framework structure, a chromium-silicon molecular sieve with a Si-O-Cr bond framework structure, or a silicon molecular sieve with two or three elements of Ti, V and Cr existing at the same time. The adsorption material is a molecular sieve with a skeleton structure and multiple elements, and has the performance of adsorbing hydrogen peroxide, wherein three elements of Ti, V and Cr have the performance of adsorbing stable hydrogen peroxide, and silica plays a role in forming a molecular sieve skeleton. For example, the titanium silicalite molecular sieve formed by uniformly distributing titanium atoms in a framework has excellent adsorption performance, and active sites for adsorbing hydrogen peroxide are four-coordinate Ti in the framework structure.
Further preferably, the content of Ti in the titanium silicalite molecular sieve is 1-5 wt%, the content of V in the vanadium silicalite molecular sieve is 1-5 wt%, the content of Cr in the chromium silicalite molecular sieve is 1-5 wt%, and the total content of two or three elements of Ti, V and Cr in the silicon molecular sieve is 1-5 wt%. For convenience of description, the three elements of Ti, V, and Cr are referred to as "hydrogen peroxide adsorbing elements" in the present invention. The content of hydrogen peroxide adsorption elements in each adsorption material is 1-5 wt%, because the adsorption efficiency is reduced due to too low content, and the difficulty of preparation technology for too high content is increased, the titanium-silicon molecular sieve, vanadium-silicon molecular sieve, chromium-silicon molecular sieve or silicon molecular sieve with the content has more excellent adsorption performance, and the preparation is more convenient and simpler.
More preferably, the titanium silicalite molecular sieve is any one of TS-1, TS-2 and HTS. The titanium-silicon molecular sieve has more excellent adsorption performance, and can adsorb hydrogen peroxide to the surface more quickly and efficiently.
Preferably, an adsorption aid for enhancing hydrogen peroxide adsorption is arranged in the container. The adsorption auxiliary agent is a substance which can form hydrogen bonds with hydrogen peroxide and an adsorption material and is not easy to decompose. Because the adsorption auxiliary agent is added into the container, the dosage of the adsorption material can be properly reduced, and the cost is reduced.
Further preferred isThe adsorption auxiliary agent is any one of 2,2,6, 6-tetramethyl-4-piperidone, 2,6, 6-tetramethyl-4-oximido-piperidine, phosphate, methanol and ethanol. Wherein the phosphate is preferably potassium dihydrogen phosphate KH2PO4Or sodium dihydrogen phosphate NaH2PO4. The adsorption aid can enhance the adsorption effect, is not easy to decompose, and can play a role for a long time.
More preferably, the amount of the 2,2,6, 6-tetramethyl-4-piperidone is 0.5-2% of the molar content of Ti in the adsorbing material, and the amount of the phosphate is 0.5-2% of the weight of the solution. The dosage of the adsorption aid is different according to different varieties, the increase of adsorption is small when the dosage is too small, and the increase of excessive adsorption effect is small.
Also further preferably, the filter membrane is a sand core filter membrane which blocks the adsorption material and the photolysis catalyst from passing through and allows water, hydrogen peroxide and the adsorption auxiliary agent to freely pass through. By adopting the sand core filter membrane, the efficiency of adsorbing hydrogen peroxide is higher, and light can be further prevented from passing through the filter membrane to irradiate the hydrogen peroxide. The hydrogen peroxide and the adsorption auxiliary agent are mutually soluble with water, and the filter membrane allows the water, the hydrogen peroxide and the adsorption auxiliary agent to freely pass through and simultaneously blocks the adsorption material and the photolysis catalyst from passing through, so that the water, the hydrogen peroxide and the adsorption auxiliary agent which freely move are arranged in the adsorption material side and the photolysis water system which are separated by the filter membrane; but the hydrogen peroxide and the adsorption auxiliary agent can move to one side of the adsorption material more and more quickly due to the adsorption property of the adsorption material, so that the hydrogen peroxide adsorption efficiency is higher.
Preferably, the filter membrane is arranged along the horizontal direction and divides the container into an upper layer and a lower layer, the photolysis water system is positioned on the upper layer of the container, and the adsorption material is positioned on the lower layer of the container. That is to say, the filter membrane separates adsorption material and photolysis water system into upper and lower two-layer, and hydrogen peroxide relies on the dead weight can be faster attached to the adsorption material surface of container lower floor like this, improves adsorption rate.
Preferably, after the adsorption material adsorbs a predetermined amount of hydrogen peroxide, the adsorption material adsorbed with hydrogen peroxide is taken out, and hydrogen peroxide is separated. The adsorbing material adsorbing hydrogen peroxide can be desorbed by water to recover hydrogen peroxide or used for some green oxidation reactions. The treated adsorbing material can be treated and then put into a container to play an adsorbing role.
Further preferably, the method of separation is centrifugation or filtration. The two methods can realize solid-liquid rapid separation, the centrifugal separation method has higher speed, and the hydrogen peroxide is less decomposed. Different centrifugation rates and times can be selected according to the properties of the adsorption material, and the principle is that the shorter the time is, the better the solid-liquid separation is ensured. Solid-liquid separation is carried out by adopting a filtration method, and hydrogen peroxide is prevented from decomposing in the separation process.
Preferably, the photolysis temperature is 10-50 ℃, and the photolysis time is 10-20 min. A large number of experimental studies show that the hydrogen peroxide adsorption efficiency is related to the photolysis temperature, the temperature is too low, and the energy consumption is increased; the decomposition of hydrogen peroxide is obviously increased and the adsorption efficiency is reduced when the temperature is too high; the photolysis temperature is controlled within the range, the energy consumption is low, the hydrogen peroxide decomposition is low, and the adsorption efficiency is high. On the other hand, the amount of hydrogen peroxide adsorption is related to the photolysis time, and the time is too short, so that the adsorption amount is too low; the time is too long, and the adsorption capacity is not increased after the adsorption saturation; the photolysis time is controlled within the range, and the adsorption amount is high.
Preferably, the light source is any one of a tungsten lamp, a quartz lamp, a mercury lamp, a hydrogen lamp, a xenon lamp, a helium lamp and a krypton lamp.
Drawings
Fig. 1 is a schematic structural diagram of a device for generating hydrogen peroxide by adsorbing a photolytic water system according to the invention.
The device comprises a container 1, a container 2, a filter membrane 3, a light source 4, a stirrer 5, an upper layer 6, a lower layer 7, a feeding and discharging port 8, a cooling liquid inlet 9, a cooling liquid outlet 10 and an adsorbing material.
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
The invention relates to a plurality of raw materials, including 2,2,6, 6-tetramethyl-4-piperidone, 2,6, 6-tetramethyl-4-oximido-piperidine, phosphate, methanol, ethanol, TiO2ZnO, these raw materials are commercially availableAnd obtaining the product by field purchase. Titanium silicalite molecular sieves such as TS-1, TS-2 and HTS can be prepared according to literature methods, and other adsorbing materials including titanium silicalite molecular sieves with Si-O-Ti bond framework structures, vanadium silicalite molecular sieves with Si-O-V bond framework structures, chromium silicalite molecular sieves with Si-O-Cr bond framework structures, or silicalite molecular sieves with two or three elements of Ti, V and Cr existing at the same time can be prepared according to literature methods. Preparation of vanadium-silicon molecular sieve: yuan Zhi Qing et al, college chemical engineering, 2002, 16 (2): 145-148; preparing a vanadium-titanium-silicon molecular sieve: bin et al, functional material, 2005, (11): 1731 to 1733; preparing a chromium-titanium-silicon molecular sieve: yuanzhi, et al, in the study of intraocular lens, 2017, (5): 855 to 860; titanium silicalite molecular sieve: smithsonian, et al, shanxi chemical, 2017, (2): 7-10, etc.
In the invention, a plurality of parameters such as weight percentage, temperature and time are uniformly marked after the unit (such as wt%, DEG C and min) is at the upper limit, for example, 1-5 wt%, 10-50 ℃ and 10-20 min. Of course, the unit can also be marked after the upper limit value and the lower limit value, such as 1 wt% -5 wt%, 10-50 ℃, 10 min-20 min. The two parameter ranges can be expressed in any way, in the embodiment, values are taken from the upper limit value, the lower limit value and the middle value of the parameter, and the numerical values are all in units. The photolysis temperature is controlled within a certain range, which indicates that the photolysis reaction can be normally carried out within the range, and a certain temperature value is not required to be defined deliberately.
The following examples are not provided to limit the scope of the present invention, nor are the steps described to limit the order of execution. Modifications of the invention which are obvious to those skilled in the art in view of the prior art are also within the scope of the invention as claimed.
As shown in figure 1, the device for adsorbing hydrogen peroxide generated by photolysis of a water system comprises a container 1, wherein a filter membrane 2 is horizontally arranged in the container 1, and the filter membrane 2 divides the container 1 into an upper layer 5 and a lower layer 6. The upper layer 5 is a photolysis water system which comprises water, a photolysis catalyst, a light source 3 and a stirrer 4, wherein the water is subjected to photolysis under the irradiation condition of the light source 3 and the catalytic action of the photolysis catalyst to generate hydrogen peroxide. An adsorbing material 10 for adsorbing hydrogen peroxide and an adsorbing aid for enhancing hydrogen peroxide adsorption are arranged in the lower layer 6. The cooling circulation system for keeping temperature is arranged on the outer side of the container 1, cooling liquid flows in the cooling circulation system, flows in from a cooling liquid inlet 8 at the bottom of the outer side of the upper container layer 5, and flows out from a cooling liquid outlet 9 at the top of the outer side of the upper container layer 5. And a feeding and discharging port 7 for feeding or taking out the adsorbing material is arranged on the outer side of the lower layer 6 of the container.
A method for adsorbing hydrogen peroxide generated by photolyzing a water system by adopting the device comprises the following specific operation processes:
1) the method comprises the following steps of (1) dividing a container 1 into an upper layer 5 and a lower layer 6 by a sand core filter membrane 2, wherein the upper layer 5 is a photolysis water system, a titanium-silicon molecular sieve HTS for adsorbing hydrogen peroxide is arranged in the lower layer 6, and an adsorption auxiliary agent 2,2,6, 6-tetramethyl-4-piperidone for enhancing hydrogen peroxide adsorption is added in the container 1;
2) starting a light source and a stirrer, so that water is subjected to photolysis under the irradiation condition of the light source and the catalytic action of a photolysis catalyst to generate hydrogen peroxide;
3) hydrogen peroxide penetrates through the filter membrane and is adsorbed on the adsorbing material, after the adsorbing material adsorbs a predetermined amount of hydrogen peroxide, the adsorbing material adsorbed with hydrogen peroxide is taken out, and the adsorbing material adsorbed with hydrogen peroxide is obtained through centrifugal separation.
The filter membrane 2 is horizontally arranged in the container 1, the container 1 is divided into an upper layer 5 and a lower layer 6 by taking the filter membrane 2 as a boundary, the photolysis water system is positioned on the upper layer 5 of the container, and the adsorption material is positioned on the lower layer 6 of the container. Certainly, the sand core filter membrane 2 can be vertically arranged in the container 1, so that the sand core filter membrane 2 divides the container 1 into a left part and a right part, one part is a photolysis water system, and the other part is filled with an adsorption material and an adsorption auxiliary agent; as the stirrer 4 arranged in the photolysis water system can enhance diffusion, hydrogen peroxide generated by the photolysis can also pass through the filter membrane 2 vertically arranged to be adsorbed on the adsorbing material.
The titanium silicalite HTS is an adsorbing material with a Si-O-Ti bond framework structure, besides HTS, TS-1, TS-2, Ti-Beta and the like can be selected as the titanium silicalite HTS, and the Ti content in the titanium silicalite HTS is 1-5 wt%. Besides the titanium-silicon molecular sieve with Si-O-Ti bond skeleton structure, the adsorption material can also be a vanadium-silicon molecular sieve with Si-O-V bond skeleton structure, a chromium-silicon molecular sieve with Si-O-Cr bond skeleton structure or a silicon molecular sieve with two or three elements of Ti, V and Cr. The vanadium-silicon molecular sieve contains 1-5 wt% of V, 1-5 wt% of Cr and 1-5 wt% of total content of two or three elements of Ti, V and Cr.
The 2,2,6, 6-tetramethyl-4-piperidone is an adsorption auxiliary agent for enhancing the adsorption of hydrogen peroxide, and the adsorption auxiliary agent can also be 2,6, 6-tetramethyl-4-oximido-piperidine, phosphate, methanol, ethanol or the like.
The sand core filter membrane can prevent the adsorption material and the photolysis catalyst from passing through, and simultaneously allows water, hydrogen peroxide and the adsorption auxiliary agent to freely pass through.
The centrifugal separation method can quickly separate out hydrogen peroxide, and can also adopt a filtering method for separation.
And water in the photolysis water system is subjected to photolysis at the temperature of 10-50 ℃ for 10-20 min, and the light source is any one of a tungsten lamp, a quartz lamp, a mercury lamp, a hydrogen lamp, a xenon lamp, a helium lamp and a krypton lamp. The photolysis catalyst is a chemical agent that increases the rate of the photolytic water reaction, such as TiO2ZnO or a supported modified photolysis water catalyst, wherein the dosage of the photolysis catalyst is determined according to different catalyst varieties, the dosage is too small, and the adsorption time is long; too much amount and high cost, and proper amount is selected to shorten the adsorption time and reduce the cost.
After the adsorption material is used for adsorbing the hydrogen peroxide in the liquid phase, the adsorption material is difficult to completely dehydrate, so the amount of the hydrogen peroxide on the adsorption material and the amount of the liquid phase are measured by an iodometry method, and the specific method comprises the following steps: centrifuging the sample taken out in the step 3) into a liquid phase and an adsorbing material phase with higher solid content, and weighing the liquid phase and the adsorbing material phase to obtain m (l) and m(s); then, the liquid phase and the adsorbing material phase are respectively titrated, and the quantity n (l) and n(s) of the adsorbed hydrogen peroxide substance are measured. In addition, according to the amount m of the adsorbent added0The mass m '(l), i.e., m' (l) ═ m(s) — m, of the liquid phase in the adsorbent phase was calculated0(ii) a Due to liquid phase H2O2The same content of (A) is as follows:
in the formula:
n (HPAM) -the amount of hydrogen peroxide substance adsorbed by the adsorption material, unit mmol;
n(s) -the amount of hydrogen peroxide substance contained in the adsorption material phase, in mmol;
n (l) -the amount of hydrogen peroxide substance contained in the liquid phase, in mmol;
m (l) -mass of liquid phase, in g;
n' (l) -the amount of hydrogen peroxide species contained in the liquid phase contained in the adsorbent phase, in mmol;
m' (l) -mass of liquid phase contained in the adsorbent phase, in g.
Example 1
A sand core filter membrane is horizontally arranged in a container to separate the container into an upper layer and a lower layer, the volume of the upper layer is 250mL, and the volume of the lower layer is 100 mL. An adsorbing material, namely titanium silicalite HTS30g (containing 13mmol of Ti) with 2.1 wt% of Ti dispersed by 50mL of deionized water, is added into the lower layer from a feeding and discharging port, and stirring magnets are placed into the lower layer. The upper layer is provided with a thermometer and a stirrer, 200mL of deionized water and 0.10g of nano ZnO are added into the upper layer, and a high-pressure mercury lamp preheated for 1 hour in advance is put into the upper layer to photolyze water. Simultaneously, the upper layer and the lower layer are started to stir, and cooling liquid is introduced outside the container. And (4) stopping photolysis for 10min, wherein the photolysis temperature is 25-30 ℃, taking out the adsorption material adsorbed with hydrogen peroxide, and performing centrifugal separation. The amount of hydrogen peroxide adsorbed in the adsorbent was determined by iodometry, with the results: adsorbing 3.8mmol of hydrogen peroxide.
The following examples in Table 1 were identical to those of example 1 except that the adsorbent was used in different amounts.
TABLE 1
The following examples in Table 2 were identical to those of example 1 except that the adsorption assistant was further added.
TABLE 2
Example 20
The photolysis temperature is controlled to be 10-15 ℃, and the result is as in example 1: adsorbing 4.1mmol of hydrogen peroxide.
Example 21
The photolysis temperature is controlled to be 45-50 ℃, and the result is as in example 1: adsorbing 2.8mmol of hydrogen peroxide.
Example 22
The photolysis time was controlled at 20min, otherwise as in example 1, with the following results: adsorbing 4.0mmol of hydrogen peroxide.
Experimental data show that the titanium silicalite molecular sieve is used as an adsorbent, adsorbed hydrogen peroxide is decomposed by about 10% within 4 days at 15 ℃, and the hydrogen peroxide is decomposed by more than 50% within 2 days at 25 ℃. Without an adsorbent system, hydrogen peroxide decomposes as soon as the concentration is high, and is also easily decomposed under illumination.
The above are merely characteristic embodiments of the present invention, and do not limit the scope of the present invention in any way. All technical solutions formed by equivalent exchanges or equivalent substitutions fall within the protection scope of the present invention.
Claims (5)
1. A method for adsorbing hydrogen peroxide generated by a photolysis water system comprises the steps that the photolysis water system comprises water, a photolysis catalyst, a light source and a stirrer, the water is subjected to photolysis under the irradiation condition of the light source and the catalytic action of the photolysis catalyst to generate hydrogen peroxide, and the method is characterized in that an adsorbing material for adsorbing the hydrogen peroxide is arranged on the outer side of the photolysis water system, the adsorbing material and the photolysis water system are arranged in the same container, and the adsorbing material and the photolysis water system are separated by a filter membrane;
the adsorption material is a titanium-silicon molecular sieve with a Si-O-Ti bond framework structure, a vanadium-silicon molecular sieve with a Si-O-V bond framework structure, a chromium-silicon molecular sieve with a Si-O-Cr bond framework structure, or a silicon molecular sieve with two or three elements of Ti, V and Cr;
an adsorption auxiliary agent for enhancing the adsorption of hydrogen peroxide is added in the container;
the filter membrane is horizontally arranged and divides the container into an upper layer and a lower layer, the photolysis water system is positioned on the upper layer of the container, and the adsorption material is positioned on the lower layer of the container;
and after the adsorption material adsorbs a predetermined amount of hydrogen peroxide, taking out the adsorption material adsorbed with the hydrogen peroxide, and separating the hydrogen peroxide.
2. The method of claim 1, wherein the Ti content of the Ti-si molecular sieve is 1 to 5 wt%, the V content of the V-si molecular sieve is 1 to 5 wt%, the Cr content of the Cr-si molecular sieve is 1 to 5 wt%, and the total content of two or three elements of Ti, V, and Cr in the si molecular sieve is 1 to 5 wt%.
3. The method of claim 1, wherein the adsorption aid is any one of 2,2,6, 6-tetramethyl-4-piperidone, 2,6, 6-tetramethyl-4-hydroxyimino-piperidine, phosphate, methanol, and ethanol.
4. The method of adsorbing hydrogen peroxide generated by a photolytic water system according to claim 1, wherein the filter membrane is a sand core filter membrane that blocks passage of the adsorption material and the photolytic catalyst, while allowing free passage of water, hydrogen peroxide, and the adsorption aid.
5. The method of adsorbing hydrogen peroxide generated by photolysis of a water system according to claim 1, wherein the method of separating the adsorption material adsorbed with hydrogen peroxide is a centrifugal separation method or a filtration method.
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