CN114289072A - Preparation method and application of magnesium sulfite catalytic oxidant - Google Patents
Preparation method and application of magnesium sulfite catalytic oxidant Download PDFInfo
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- CN114289072A CN114289072A CN202210026130.7A CN202210026130A CN114289072A CN 114289072 A CN114289072 A CN 114289072A CN 202210026130 A CN202210026130 A CN 202210026130A CN 114289072 A CN114289072 A CN 114289072A
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Abstract
The invention discloses a preparation method and application of a magnesium sulfite catalytic oxidant, and belongs to the technical field of solid waste recycling. The preparation method of the magnesium sulfite catalytic oxidant comprises the following steps: dissolving 1, 2, 4-trimellitic acid and metal salt (cobalt salt and/or iron salt), adding triethylamine, and performing ultrasonic reaction to obtain the magnesium sulfite catalytic oxidant. The catalytic rate of the catalyst magnesium sulfite prepared by the invention reaches 0.12mmol (L.s)‑1And the present invention isThe preparation method is simple, has small investment, easy operation and small secondary pollution, and can be used for catalytic oxidation of the byproduct magnesium sulfite generated in magnesium desulphurization.
Description
Technical Field
The invention relates to the technical field of solid waste recycling, in particular to a preparation method and application of a magnesium sulfite catalytic oxidant.
Background
Wet Flue Gas Desulfurization (WFGD) is the current stage SO2The main pollution control technology is the only desulphurization mode for large-scale commercial application in the world, and at the same time, the main pollution control technology occupies an important position in economic benefit and technical maturity. Currently controlling SO2The discharged wet desulphurization process mainly comprises the following steps: a dual alkali flue gas desulfurization technology, a limestone-gypsum wet desulfurization technology, a magnesium oxide flue gas desulfurization technology, an ammonia desulfurization technology and the like.
The wet magnesium desulfurization mostly adopts a hedging gas-liquid two-phase flow reaction mode, so that the desulfurization efficiency is high, the desulfurization efficiency can reach more than 98 percent by verification, the technology is mature, and the operation reliability is higher. The operation cost is low, the same sulfur dioxide is removed, and the dosage of the magnesium oxide is only 40 percent of that of the limestone method calcium carbonate. However, one of the common problems in wet flue gas desulfurization is the recycling and resource problem of sulfite as a desulfurization byproduct, and due to the problems of too complex byproduct components, too high content of harmful substances such as heavy metals, and treatment technical limitations, most desulfurization byproducts can be disposed only by landfill disposal, and only a small amount of desulfurization byproducts can be processed and then used in the fields of building materials, soil improvement, agricultural fertilizers, and the like. Most of desulfurization by-products, namely sulfite, are treated in a non-catalytic oxidation mode, and the oxidation efficiency is low. Therefore, related organizations and scholars will study the shift of the center of gravity to the development of catalysts.
In the process of adding a catalyst (metal ions) to carry out catalytic oxidation reaction on the sulfite, the sulfite oxidation is carried out according to the following process:
SO3 2-+MeZ+→·SO3 2-+Me(Z-1)+；
·SO3 2-+O2→·SO5 -；
SO3 2-+·SO5 -→SO3 -+·SO5 2-；
SO3 2-+·SO5 2-→2SO4 2-。
in the research on sulfite catalytic oxidation, the catalysts with good catalytic effect are generally transition metals (such as manganese, cobalt, copper, iron, etc.), and sometimes the synergistic catalytic effect of two or more metal ions is more significant. For example, chinese patents CN107185581A, CN110420659A, and CN110237864A all disclose methods of magnesium sulfite catalysts, which achieve catalytic oxidation while increasing the catalytic rate, but the operation steps are complicated and the operation cost is high. How to increase the catalytic rate, simplify the operation steps and reduce the operation cost becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to provide a preparation method and application of a magnesium sulfite catalytic oxidant, a catalyst with higher catalytic rate is prepared by adjusting raw materials and the preparation method, the required process equipment and process are simple to control, the economic cost is low, the environmental benefit is high, and multiple purposes are achieved at one stroke, so that the magnesium sulfite catalytic oxidation technology is more economic and effective, and a new way is developed for the treatment and recycling of magnesium sulfite desulfurized by a magnesium method.
In order to achieve the purpose, the invention provides the following scheme:
one of the technical schemes of the invention is as follows: a preparation method of a magnesium sulfite catalytic oxidant comprises the following steps: dissolving benzene tricarboxylic acid and metal salt, adding triethylamine, and performing ultrasonic reaction to obtain the magnesium sulfite catalytic oxidant;
the metal salt is cobalt salt and/or iron salt.
Further, the benzene tricarboxylic acid comprises 1, 2, 4-trimellitic acid or 1, 3, 5-trimesic acid.
Further, the cobalt salt is CoCl2·6H2O; the iron salt is FeCl3·6H2O。
Further, the molar ratio of the 1, 2, 4-trimellitic acid to the metal salt is 1: 1.
further, when the metal salt is cobalt salt and iron salt, the molar ratio of the cobalt salt to the iron salt is 1-3: 1.
further, the time of ultrasonic treatment is 6-10 h.
Further, the solvents used for the dissolution include DMF, ethanol and water.
Further, after the ultrasonic reaction, centrifuging at a speed of 5000 r/min-9000 r/min to collect a product, washing with ethanol, and drying at 50-80 ℃ for 12h to obtain the magnesium sulfite catalytic oxidant.
The second technical scheme of the invention is as follows: the magnesium sulfite catalytic oxidant prepared by the preparation method.
The third technical scheme of the invention is as follows: the application of the magnesium sulfite catalytic oxidant in the treatment and recovery of magnesium sulfite.
The invention discloses the following technical effects:
the novel magnesium sulfite catalytic oxidant prepared by the invention is a complex of Co/Fe and 1, 2, 4-trimellitic acid, and the complex catalyzes and oxidizes magnesium sulfite under the condition of air atmosphere, wherein the catalytic rate is 0.12mmol (L.s) under the conditions that the catalyst is 0.1g, the magnesium sulfite is 50g/L, the operation temperature is 35-65 ℃, the air flow rate is 1L/min, and the pH value is 6-10-1. The method has the advantages of simple process, low investment, easy operation and low secondary pollution, and can be used for catalytic oxidation of the byproduct magnesium sulfite in magnesium desulphurization.
The novel magnesium sulfite catalytic oxidant prepared by the invention has 3d7Electronically configured Co2+Can contain delocalized SO3 2-Remote electron, thus in SO3 2-To generate electron holes. Thus generating SO3-The free radicals of (a) initiate the following chain reaction:
the chain reaction starts: SO (SO)3 2-+Co2+→·SO3 -+Co-；
Preparation of chain reaction: SO3 -+O2→·SO5 -；
·SO5 -+SO3 2-→SO5 2-+·SO3 -；
Product formation: SO (SO)5 2-+SO3 2-→2SO4 2-；
Terminating the chain reaction: SO5 -+·SO5 -→ internal products; therefore, the catalytic rate is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a flow chart of a device for preparing a magnesium sulfite catalytic oxidant for catalytic reaction according to an embodiment of the invention.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The raw materials in the following examples were all subjected to a roasting treatment before melting.
Example 1
A preparation method of a magnesium sulfite catalytic oxidant comprises the following steps:
1, 2, 4-trimellitic acid (TMLA, 0.75mmol), CoCl2·6H2O (0.5625mmol) and FeCl3·6H2O (0.1875mmol) was dissolved in a mixed solution of DMF (32mL), ethanol (2mL) and deionized water (2mL), followed by the addition of triethylamine (0.8mL), stirring for 5min and then continuous sonication at room temperature for 8h, centrifugation at 7000r/min to collect the product, washing three times with ethanol and drying at 60 ℃ for 12h to give magnesium sulfite catalytic oxidant.
Example 2
The difference from example 1 is that CoCl is added2·6H2O (0.5625mmol) andFeCl3·6H2replacement of O (0.1875mmol) by CoCl2·6H2O(0.75mmol)。
Example 3
The difference from example 1 is that CoCl is added2·6H2O (0.5625mmol) and FeCl3·6H2Replacement of O (0.1875mmol) by CoCl2·6H2O (0.375mmol) and FeCl3·6H2O(0.375mmol)。
Example 4
The difference from example 1 is that CoCl is added2·6H2O (0.5625mmol) and FeCl3·6H2Replacement of O (0.1875mmol) by FeCl3·6H2O(0.75mmol)。
Comparative example 1
1, 2, 4-trimellitic acid (TMLA, 0.5mmol), CoCl2·6H2O (0.5625mmol) and FeCl3·6H2O (0.1875mmol) was dissolved in a mixed solution of DMF (32mL), ethanol (2mL) and deionized water (2mL), followed by the addition of triethylamine (0.8mL), stirring for 5min and then continuous sonication at room temperature for 8h, centrifugation at 7000r/min to collect the product, washing three times with ethanol and drying at 60 ℃ for 12h to give magnesium sulfite catalytic oxidant.
The content of Co-Fe in the prepared catalyst is increased, and the amount of active metal is larger than the number of binding sites on trimellitic acid.
Comparative example 2
The difference from example 1 is that the sonication time was 4 h.
When the prepared catalyst is washed by ethanol, the loss of active metal Co is serious, and the conversion rate of catalytic reaction is reduced.
Comparative example 3
The same as in example 2, except that 1, 2, 4-trimellitic acid (TMLA, 0.75mmol) was replaced by 1, 3, 5-trimesic acid (BTC, 0.75 mmol).
Effect example 1
The equipment flow chart is shown in figure 1, wherein 1 in figure 1 is a nitrogen storage tank, 2 is an oxygen storage tank, 3 is a mass flow meter, 4 is an air compressor, 5 is a control valve, 6 is a gas mixing tank, 7 is a constant temperature water bath kettle, 8 is a reaction device, 9 is a pH meter, and 10 and 11 are volumetric flasks.
Adding 200mL of deionized water into a beaker, placing the beaker (reaction device) in a 45 ℃ constant-temperature water bath kettle, introducing the gas in a gas mixing tank into the beaker at the speed of 1L/min, opening magnetic stirring (200r/min), adding 0.1g of magnesium sulfite catalytic oxidant (prepared in example 2) into the beaker after the temperature is stable, and then adding 10g of MgSO 23And timing, keeping the pH value of the aqueous solution to be 8 (monitoring the pH value by using a pH meter, adjusting the pH value by using 1mol/L NaOH in a volumetric flask 10 and 1mol/L HCl in a volumetric flask 11), taking 2.5mL (solution 1) of the aqueous solution when the pH value is 5min, taking 2mL (solution 2) of the aqueous solution when the pH value is 10min, taking 1.5mL (solution 3) of the aqueous solution when the pH value is 15min, taking 1mL (solution 4) of the aqueous solution when the pH value is 20min, taking 0.6mL (solution 5) of the aqueous solution when the pH value is 25min, taking 0.3mL (solution 6) of the aqueous solution when the pH value is 35min, placing 1-6 of the aqueous solution into 100mL volumetric flasks respectively, adding 1 mL: 1, shaking up with constant volume. 50mL of the solution was transferred from the measuring cylinder and placed in a 100mL glass, 2.5mL of the stabilizing solution was added, the solution was placed on a magnetic stirrer, and 0.2g of BaCl was added2Stirring for 1min, standing for 4min, measuring absorbance at 420nm wavelength of a spectrophotometer, and recording data;
in the catalytic reaction process, air compressed by an air compressor is introduced into a gas mixing tank, and the inflow speed of the air is controlled by a mass flow meter 3 to provide air atmosphere for the catalytic reaction;
when doing the oxygen partial pressure experiment, through mass flow meter 3 and air compressor, let in gas blending tank 6 with nitrogen gas from nitrogen gas holding vessel 1, oxygen lets in gas blending tank 6 from oxygen gas holding vessel 2, controls the speed that oxygen, nitrogen gas flowed into gas blending tank 6 through mass flow meter 3 and control valve 5, and wherein the mass ratio of nitrogen gas and oxygen is 8: 2, the oxygen content was controlled from 0 to 21% to investigate the effect of oxygen on the catalytic reaction.
The preparation method of the stabilizer comprises the following steps: weighing 75g of NaCl, dissolving in 300mL of deionized water, adding 30mL of concentrated HCl, 50mL of glycerol (glycerin) and 100mL of absolute ethyl alcohol, and uniformly mixing;
the preparation method of 1:1HCl comprises the following steps: and mixing concentrated hydrochloric acid and deionized water in equal volume.
Calculating the catalytic oxidation rate:
k: to show the degree of conversion (mol. L) of magnesium sulfite to magnesium sulfate under different reaction conditions-1·s-1)
CS(IV),t: represents the concentration (mol. L) of sulfate radical at time t-1)
CS(IV),t0: is represented at time t0Concentration (mol. L) of sulfate radical at the time of-1) The concentration at which the reaction starts is generally 0.
The catalytic oxidation rate was calculated to be 0.12mmol (L.s)-1。
The catalyst was replaced with the magnesium sulfite catalytic oxidant prepared in example 1, and the catalytic oxidation rate was 0.098mmol (L.s) under otherwise unchanged reaction conditions-1；
The catalyst was replaced with the magnesium sulfite catalytic oxidant prepared in example 3, and the catalytic oxidation rate was 0.092mmol (L.s) under otherwise unchanged reaction conditions-1；
The catalyst was replaced with the magnesium sulfite catalytic oxidant prepared in example 4, and the catalytic oxidation rate was 0.012mmol (L.s) with the other reaction conditions unchanged-1；
Replacing the catalyst with the magnesium sulfite catalytic oxidant prepared in the proportion 3, keeping other reaction conditions unchanged, and ensuring that the catalytic oxidation rate is 0.089mmol (L.s)-1。
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (9)
1. The preparation method of the magnesium sulfite catalytic oxidant is characterized by comprising the following steps: dissolving benzene tricarboxylic acid and metal salt, adding triethylamine, and performing ultrasonic reaction to obtain the magnesium sulfite catalytic oxidant;
the metal salt is cobalt salt and/or iron salt.
2. The method of claim 1, wherein said benzene tricarboxylic acid comprises 1, 2, 4-trimellitic acid or 1, 3, 5-trimesic acid.
3. The method of claim 1, wherein the cobalt salt is CoCl2·6H2O; the iron salt is FeCl3·6H2O。
4. The method for preparing the magnesium sulfite catalytic oxidant according to claim 1, wherein the molar ratio of the 1, 2, 4-trimellitic acid to the metal salt is 1: 1.
5. the preparation method of the magnesium sulfite catalytic oxidant according to claim 1, wherein when the metal salts are cobalt salts and iron salts, the molar ratio of the cobalt salts to the iron salts is 1-3: 1.
6. the preparation method of the magnesium sulfite catalytic oxidant according to claim 1, wherein the ultrasonic treatment time is 6-10 h.
7. The method of claim 1, wherein the solvent used for dissolving comprises DMF, ethanol and water.
8. The magnesium sulfite catalytic oxidant prepared by the preparation method of any one of claims 1 to 7.
9. Use of the magnesium sulfite catalytic oxidant of claim 8 in magnesium sulfite treatment and recovery.
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Cited By (1)
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