CN114314772A - Resource utilization process of salt residues in beta-aminopropionic acid production - Google Patents
Resource utilization process of salt residues in beta-aminopropionic acid production Download PDFInfo
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Abstract
The invention discloses a resource utilization process of salt residues in beta-aminopropionic acid production, which comprises the following steps: after sodium sulfate residue containing organic matters such as beta-aminopropionic acid is dissolved in water, under the action of a catalyst and an additive, COD is reduced through electrochemical advanced oxidation, and then anhydrous sodium sulphate is prepared through post-treatment. Wherein the catalyst is a supported metal catalyst, and comprises a silicon dioxide carrier, and iron and platinum existing in the form of metal or oxide; the additive is a peroxy acid; the electrochemical advanced oxidation adopts a boron-doped diamond anode modified by metal. The process greatly improves the efficiency of electrochemical oxidation, has the COD removal rate of more than 99 percent, and has the advantages of good stability, low cost and the like. The process avoids the problems of high energy consumption, high cost and the like of salt residue incineration treatment in beta-aminopropionic acid production, realizes resource utilization of sodium sulfate residue, and greatly improves the added value.
Description
Technical Field
The invention belongs to the field of production solid waste treatment, and particularly relates to a resource utilization process of salt residues in beta-aminopropionic acid production.
Background
The beta-aminopropionic acid is used as a key intermediate for synthesizing calcium pantothenate, and has wide market demand. In the process of preparing beta-aminopropionitrile by hydrolyzing beta-aminopropionitrile, a large amount of sodium sulfate is generated, and the generated large amount of sodium sulfate inevitably contains organic matters such as beta-aminopropionic acid, so that the quality of the sodium sulfate is greatly limited. The prior method is used for incineration treatment as solid waste and has the defects of high energy consumption, high pollution and the like. Therefore, development of a green treatment method for improving the additional value of sodium sulfate is imperative.
Electrochemical oxidation technology has received more and more attention because of its advantages such as green, high efficiency, easy operation. The method realizes the nondifferential degradation of organic matters by generating active intermediate products, such as hydroxyl free radicals and the like, on the surface of an anode. The properties of the anode material play a decisive role in the performance of catalysis, and among various inactive electrodes, the boron-doped diamond electrode is considered to be the electrode with the most potential in the field.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a resource utilization process of salt residues in beta-aminopropionic acid production. The process greatly improves the efficiency of electrochemical oxidation, has the COD removal rate of more than 99 percent, and has the advantages of good stability, low cost and the like. The process avoids the problems of high energy consumption, high cost and the like of salt residue incineration treatment in beta-aminopropionic acid production, realizes resource utilization of sodium sulfate residue, and greatly improves the added value.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
after sodium sulfate residue containing organic matters such as beta-aminopropionic acid is dissolved in water, under the action of a catalyst and an additive, COD is reduced through electrochemical advanced oxidation, and then anhydrous sodium sulphate is prepared through post-treatment.
The sodium sulfate residue generally has an organic content of 0.5 to 5.0 wt%.
The catalyst is a supported metal catalyst, and comprises a silica carrier and iron and platinum which exist in the form of metal or oxide. Wherein the mass of the silicon dioxide carrier is taken as a reference, the contents of iron and platinum are as follows:
10-30 wt.%, preferably 17-24 wt.% of platinum;
iron 2-8 wt.%, preferably 3-6 wt.%.
The catalyst may be prepared by methods conventional in the art.
The addition amount of the catalyst is 0.5-4.5 wt% of the mass of the sodium sulfate residue.
The additive is selected from one or more of performic acid, peracetic acid, peroxypropionic acid and peroxybenzoic acid; the addition amount of the additive is 1-10 wt% of the mass of the sodium sulfate residue.
The invention relates to a boron-doped diamond anode modified by transition metal for electrochemical advanced oxidation, which is prepared by the following steps:
(1) the boron-doped diamond film is prepared by a hot wire vapor deposition method by taking methane with the volume ratio of 0.1-5% as a carbon source, hydrogen as etching gas and boron trioxide as a boron source, wherein the deposition temperature is 650-900 ℃.
(2) And (3) placing the boron-doped diamond film in the transition metal electrodeposition liquid, and carrying out electroplating treatment, washing and drying to obtain the transition metal modified boron-doped diamond anode.
The transition metal in the preparation of the electrode is selected from at least two of iron, cobalt, platinum, osmium and iridium, the proportional relationship between the two elements is not particularly required, and in some specific embodiments, the mass ratio is preferably controlled to be 1-5: 1;
the electroplating treatment in the step (2) adopts a ruthenium iridium electrode and a titanium plate electrode, the working voltage is 1.5-3.5V, and the electroplating time is 5-10 min; the washing solvent is a mixed solvent of ethanol and acetonitrile, and the drying temperature is 70-120 ℃.
The boron-carbon ratio in the transition metal modified boron-doped diamond anode prepared by the invention is 1:1000-10000, preferably 1: 3500-6000; the mass fraction of the transition metal is 0.1-4.0%, preferably 0.3-2.5%.
Dissolving sodium sulfate residue containing organic matters such as beta-aminopropionic acid and the like in water according to the mass ratio of 1:1-5, preferably 1: 2-4;
the conditions of the electrochemical advanced oxidation are as follows: the cathode adopts a titanium electrode, the pH value of the system is 5-9, the voltage is 1-3V, and the electrolysis time is 7-15 h.
The post-treatment of the invention comprises the steps of filtering and recovering the catalyst, distilling and drying.
The method has the advantages that the use of the process greatly improves the efficiency of electrochemical oxidation, the COD removal rate is more than 99%, and the method has the advantages of good stability, low cost and the like. The process avoids the problems of high energy consumption, high cost and the like of salt residue incineration treatment in beta-aminopropionic acid production, realizes resource utilization of sodium sulfate residue, and greatly improves the added value.
Detailed Description
The present invention is further illustrated below with reference to specific examples, it being noted that the scope of the present invention includes, but is not limited to, the examples listed.
Example 1
The boron-doped diamond film is prepared by a hot wire vapor deposition method, the volume ratio of methane is controlled to be 1.2%, the boron-carbon ratio is controlled to be 1:6000, the deposition temperature is 750 ℃, and the growth time is 8 hours. Weighing ferric chloride, platinum chloride and boron-doped diamond for later use, and controlling the mass ratio of the iron center to the platinum center to the boron-doped diamond to be 0.5:0.5: 99. Dissolving ferric chloride and platinum chloride in water to prepare an electrodeposition solution, respectively using the boron-doped diamond, the ruthenium iridium electrode and the titanium plate electrode as a working electrode, a counter electrode and a reference electrode, wherein the working voltage is 1.7V, the electroplating time is 7min, washing by using an ethanol/acetonitrile mixed solution, and drying at 90 ℃ to prepare the transition metal modified boron-doped diamond anode.
According to the technical scheme, ferric chloride and platinum chloride with the active metal center mass ratio of 5:20 are weighed and mixed to serve as metal salt for later use, wherein the ferric accounts for 5% of silicon dioxide, and the platinum accounts for 20% of the silicon dioxide. The metal salt, the silicon dioxide and the water are stirred, mixed evenly and then are fully immersed for 3 hours, dried at 70 ℃ and roasted at 350 ℃ to prepare the required catalyst.
Dissolving sodium sulfate residue (the content of organic matters such as beta-aminopropionic acid is 1.95 wt%) and water according to the mass ratio of 1:3, wherein the addition amounts of the catalyst and the peroxyacetic acid are respectively 1.5 wt% and 2.5 wt% of the mass of the sodium sulfate residue, and transferring the materials into an electrolytic cell. The prepared boron-doped diamond modified by the transition metal is taken as an anode, a titanium plate is taken as a cathode, the pH value of the system is 6.5, the working voltage is 1.7V, and the electrolysis time is 9 h. The COD removal rate is 99.1 percent through detection.
Example 2
The boron-doped diamond film is prepared by a hot wire vapor deposition method, the volume ratio of methane is controlled to be 3.5%, the ratio of boron to carbon is controlled to be 1:5000, the deposition temperature is 850 ℃, and the growth time is 7 hours. Weighing cobalt chloride, iridium chloride and boron-doped diamond for later use, and controlling the mass ratio of the cobalt center to the iridium center to the boron-doped diamond to be 1.0:0.5: 98.5. Dissolving cobalt chloride and iridium chloride in water to prepare an electrodeposition solution, respectively using the boron-doped diamond, ruthenium iridium electrode and titanium plate electrode as a working electrode, a counter electrode and a reference electrode, wherein the working voltage is 2.5V, the electroplating time is 9min, washing by using an ethanol/acetonitrile mixed solution, and drying at 80 ℃ to obtain the transition metal modified boron-doped diamond anode.
According to the weight ratio of iron to silicon dioxide of 4% and platinum to silicon dioxide of 23%, weighing ferric chloride and platinum chloride with the active metal center mass ratio of 4:23, and mixing them to obtain metal salt for later use. The metal salt, the silicon dioxide and the water are stirred, mixed evenly and then are fully immersed for 3 hours, dried at 75 ℃ and roasted at 450 ℃ to prepare the required catalyst.
Dissolving sodium sulfate residue (the content of organic matters such as beta-aminopropionic acid is 1.35 wt%) and water according to the mass ratio of 1:2, wherein the addition amount of the catalyst and the peroxyacetic acid are respectively 1.0 wt% and 2.0 wt% of the mass of the sodium sulfate residue, and transferring the materials into an electrolytic cell. The prepared boron-doped diamond modified by platinum group metal is taken as an anode, a titanium plate is taken as a cathode, the pH value of the system is 7.0, the working voltage is 2.1V, and the electrolysis time is 12 h. The COD removal rate is 99.3 percent through detection.
Example 3
The boron-doped diamond film is prepared by a hot wire vapor deposition method, the volume ratio of methane is controlled to be 2.5 percent, the ratio of boron to carbon is controlled to be 1:4000, the deposition temperature is 850 ℃, and the growth time is 5 hours. Weighing iridium chloride, osmium chloride and boron-doped diamond for later use, and controlling the mass ratio of the iridium center to the osmium center to the boron-doped diamond to be 1.5:1.0: 97.5. Dissolving iridium chloride and osmium chloride in water to prepare an electrodeposition solution, respectively using boron-doped diamond, ruthenium iridium electrodes and titanium plate electrodes as a working electrode, a counter electrode and a reference electrode, wherein the working voltage is 1.9V, the electroplating time is 7min, washing by using an ethanol/acetonitrile mixed solution, and drying at 100 ℃ to prepare the transition metal modified boron-doped diamond anode.
Weighing ferric chloride and platinum chloride with the active metal center mass ratio of 6:18 according to the proportion that iron accounts for 6% of silicon dioxide and platinum accounts for 18% of silicon dioxide, and mixing the ferric chloride and the platinum chloride to obtain metal salt for later use. The metal salt, the silicon dioxide and the water are stirred, mixed evenly and then fully immersed for 3 hours, dried at 85 ℃ and roasted at 400 ℃ to prepare the required catalyst.
Dissolving sodium sulfate residue (the content of organic matters such as beta-aminopropionic acid is 0.85 wt%) and water at a mass ratio of 1:1, wherein the addition amounts of the catalyst and the peroxopropionic acid are 0.5 wt% and 3.5 wt% of the mass of the sodium sulfate residue, respectively, and transferring the above materials into an electrolytic cell. The prepared boron-doped diamond modified by platinum group metal is taken as an anode, a titanium plate is taken as a cathode, the pH value of the system is 7.5, the working voltage is 1.9V, and the electrolysis time is 15 h. The COD removal rate is 99.2% by detection.
Comparative example
The transition metal modified boron-doped diamond anode was prepared as in example 1. The catalyst preparation method of example 1 was used to prepare a catalyst having both iron and platinum contents of 6 wt%. By the same process investigation, the COD removal rate is only 30.2 percent through detection.
The above embodiments are not intended to limit the technical solutions of the present invention in any way. Any simple modification, equivalent change and modification made to the above embodiments according to the technical spirit of the present invention fall within the scope of the present invention.
Claims (10)
1. A resource utilization method of salt residues in beta-aminopropionic acid production comprises the following steps: after sodium sulfate residue containing beta-aminopropionic acid is dissolved in water, under the action of catalyst and additive, COD is reduced by electrochemical advanced oxidation, and then anhydrous sodium sulphate is prepared by post-treatment.
2. The process of claim 1 wherein the catalyst is a supported metal catalyst comprising a silica support and iron and platinum in the form of a metal or oxide.
3. The process according to claim 1 or 2, characterized in that the composition of iron and platinum in the catalyst, based on the mass of the silica support, is:
10-30 wt.%, preferably 17-24 wt.% of platinum;
iron 2-8 wt.%, preferably 3-6 wt.%;
preferably, the catalyst is added in an amount of 0.5 to 4.5 wt% based on the mass of the sodium sulfate residue.
4. A process according to any one of claims 1 to 3, wherein the additive is selected from one or more of performic acid, peracetic acid, peroxopropionic acid, perbenzoic acid;
preferably, the additive is added in an amount of 1 to 10 wt% based on the mass of the sodium sulfate residue.
5. The method according to any one of claims 1 to 4, wherein the electrochemical advanced oxidation is carried out using a boron-doped diamond anode modified with a transition metal, preferably the transition metal is selected from at least two of iron, cobalt, platinum, osmium, iridium, more preferably the transition metal is present in a mass fraction of 0.1 to 4.0%.
6. The method of claim 5, wherein the transition metal modified boron-doped diamond anode is prepared by:
(1) preparing the boron-doped diamond film by a hot wire vapor deposition method by taking methane with the volume ratio of 0.1-5% as a carbon source, hydrogen as etching gas and boron trioxide as a boron source, wherein the preferable deposition temperature is 650-;
(2) and (3) placing the boron-doped diamond film in the transition metal electrodeposition liquid, and carrying out electroplating treatment, washing and drying to obtain the transition metal modified boron-doped diamond anode.
7. The method as claimed in claim 6, wherein the boron-carbon ratio in the prepared transition metal modified boron-doped diamond anode is 1:1000-10000, preferably 1: 3500-6000.
8. The method according to claim 6, wherein the plating treatment of step (2) adopts ruthenium iridium electrode and titanium plate electrode, the working voltage is 1.5-3.5V, and the plating time is 5-10 min; the drying temperature is 70-120 ℃.
9. The method according to any one of claims 1 to 8, wherein the sodium sulfate residue is dissolved in water in a mass ratio of 1:1 to 5.
10. The method according to any one of claims 1 to 9, wherein the conditions of the electrochemical advanced oxidation are: the cathode adopts a titanium electrode, the pH value of the system is 5-9, the voltage is 1-3V, and the electrolysis time is 7-15 h.
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KR20130078834A (en) * | 2011-12-31 | 2013-07-10 | 바다정수산업(주) | Treating and reusing method of high salinity waste water |
CN106830465A (en) * | 2017-01-16 | 2017-06-13 | 中科合成油技术有限公司 | Point salt and the method for purifying and recycling of a kind of brine waste |
CN108558146A (en) * | 2018-06-13 | 2018-09-21 | 江苏湖大化工科技有限公司 | Process and device associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater |
CN110643972A (en) * | 2019-09-29 | 2020-01-03 | 哈尔滨工业大学 | Preparation method and application of gold nanoparticle modified boron-doped diamond electrode |
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Publication number | Priority date | Publication date | Assignee | Title |
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KR20130078834A (en) * | 2011-12-31 | 2013-07-10 | 바다정수산업(주) | Treating and reusing method of high salinity waste water |
CN106830465A (en) * | 2017-01-16 | 2017-06-13 | 中科合成油技术有限公司 | Point salt and the method for purifying and recycling of a kind of brine waste |
CN108558146A (en) * | 2018-06-13 | 2018-09-21 | 江苏湖大化工科技有限公司 | Process and device associated with organic matter advanced oxidation and electrolytic catalysis in a kind of high-salt wastewater |
CN110643972A (en) * | 2019-09-29 | 2020-01-03 | 哈尔滨工业大学 | Preparation method and application of gold nanoparticle modified boron-doped diamond electrode |
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