CN110724968B - Industrial production method of hydroiodic acid - Google Patents
Industrial production method of hydroiodic acid Download PDFInfo
- Publication number
- CN110724968B CN110724968B CN201810780327.3A CN201810780327A CN110724968B CN 110724968 B CN110724968 B CN 110724968B CN 201810780327 A CN201810780327 A CN 201810780327A CN 110724968 B CN110724968 B CN 110724968B
- Authority
- CN
- China
- Prior art keywords
- anode
- iodide
- iodine
- cathode
- hydroiodic acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
Abstract
The invention belongs to the field of chemical synthesis, and in particular relates to an industrial production method of hydriodic acid, which takes iodine, soluble iodide, soluble alkali or soluble oxysalt and water as raw materials, takes an electric synthesis unit tank consisting of an electrode, an electrode support component, a bipolar membrane and a tank body as synthesis equipment, and carries out the production of the hydriodic acid by an electrochemical synthesis method.
Description
Technical Field
The invention belongs to the technical field of green synthesis of hydroiodic acid, and particularly relates to an industrial production method of hydroiodic acid.
Technical Field
The hydroiodic acid is an iodine inorganic strong acid and has the following purposes:
(1) High-end catalyst: the hydroiodic acid is used as efficient catalyst for synthesizing acetic acid through methanol carbonylation process. Acetic acid is an important basic chemical raw material, is widely used in the fields of chemical industry, light industry, textile, medicine, printing and dyeing, rubber, pesticide, electronics, food and the like, and has important significance to national economy.
(2) New material fields such as graphene, integrated circuit industry: graphene is a new material with great application potential and national emphasis on encouraging development. Hydroiodic acid is used as a strong reducing agent for preparing graphene films, graphene fibers, graphene-based flexible conductive materials, graphene-coated glass fibers and the like. In the integrated circuit industry, hydroiodic acid is used as an etchant for integrated circuits and also in ion implantation processes in the fabrication of semiconductor devices. Hydroiodic acid is also used in the manufacture of perovskite semiconductor materials (e.g., thin film perovskite solar cells).
(3) Preparing high-purity iodide: hydroiodic acid is an iodine source for preparing high purity iodides. High-purity iodides (lithium iodide, rhodium iodide, potassium iodide, calcium iodide and the like) are important raw materials essential for various fields such as lithium batteries, catalysts, fine chemical engineering, liquid crystals, semiconductors, medicines, pesticides, development, reagents and the like. The use of hydriodic acid changes the traditional route to iodide directly from iodine. Taking potassium iodide as an example, the traditional method takes iodine and potassium hydroxide as raw materials, and then iron powder and potassium carbonate or formic acid are added to participate in the reaction. The method has complex reaction, low yield, high impurity content of finished potassium iodide and great amount of waste such as iron carbonate which pollutes the environment. The hydroiodic acid is used as an iodine source to react with potassium hydroxide, namely, the potassium iodide and water are directly obtained, namely, the salt and the water are generated by simple acid-base reaction, and the purity of the finished product potassium iodide is greatly improved due to less substances participating in the reaction and high purity.
(4) Other uses: other uses of hydroiodic acid also include: medical intermediates, disinfectants, raw materials for dyes and fragrances, analytical reagents, reducing agents in organic chemistry, and the like.
The traditional method for producing the hydriodic acid is a red phosphorus method, and the specific production process is that iodine and red phosphorus are respectively and slowly added into a reactor filled with water, and react under heating and stirring, so that phosphorous acid or a solution of phosphoric acid and hydriodic acid can be generated according to different iodine usage. Filtering the solution after the reaction, heating and distilling the filtrate, and collecting fractions at 125-130 ℃ to prepare 57% hydriodic acid solution. If free I2 exists, water is added to dilute before distillation, heating is carried out to boil, then 50% hypophosphorous acid is added until the color of iodine disappears, and then distillation is carried out.
The reaction equation is as follows:
2P+3I 2 +6H 2 O＝2H 3 PO 3 +6HI
2P+5I 2 +8H 2 O＝2H 3 PO 4 +10HI
as can be seen from the reaction equation, red phosphorus is needed in the method, the phosphorus belongs to inflammable substances, side reactions exist in the reaction, substances such as phosphine, tetra hydro phosphide and the like are possibly generated under the heating condition, the phosphine is a highly toxic and easy-spontaneous combustion gas, and the suction of the phosphine can influence the heart, the respiratory system, the kidney, the intestines and stomach, the nervous system and the liver. The diphosphorus tetrahydrochysene is a natural substance and has a certain safety risk.
The use of phosphorus also produces waste liquid containing phosphoric acid and phosphorous acid, and the waste liquid is finally treated as dangerous waste, so that the problems of environmental protection and safety exist.
The electrochemical synthesis of hydroiodic acid has been reported in literature, but the synthesis reaction unit is three-chamber and multi-chamber, and has the disadvantages of complex operation, extremely high equipment cost, difficult control and the like.
Therefore, a need exists for a simple, easy-to-implement, safe, environment-friendly method for preparing hydroiodic acid with low manufacturing cost and high product purity, which is one of the problems to be solved in the art.
Disclosure of Invention
The invention takes iodine, soluble iodide, soluble alkali or soluble oxysalt and water as raw materials, takes an electrosynthesis unit tank consisting of an electrode, an electrode supporting component, a bipolar membrane and a tank body as synthesis equipment, and carries out the production of the hydroiodic acid by an electrochemical synthesis method.
In the synthesis process, only iodine and water are used for chemical reaction, and the soluble iodide, the soluble alkali solution or the soluble oxysalt can be recycled, so that the reaction raw materials are purer, and the purity of the target product is higher. The production process uses electricity as a synthesis driving force, dangerous red phosphorus is not used, and the synthesis is carried out at a lower temperature and normal pressure, so that the safety of the method for producing the hydriodic acid is greatly improved, meanwhile, waste liquid of dangerous waste phosphoric acid and phosphorous acid is not produced, the cost for treating the dangerous waste is avoided, and the environmental protection pressure is greatly reduced.
The main technical scheme of the invention is as follows:
an industrial production method of hydroiodic acid is implemented according to the following steps:
the invention first employs an electrosynthesis cell apparatus comprising
(1) Two reaction chambers separated by a bipolar membrane;
(2) The cathode electrode plate and the anode electrode plate are respectively arranged at two sides of the bipolar membrane; the cathode plate is provided with a cathode groove at one side, and a catholyte is placed in the cathode groove, wherein the catholyte consists of an aqueous solution containing iodine and soluble iodide; the anode plate is provided with an anode groove at one side, and a soluble alkali solution or a soluble oxysalt solution is put in the anode groove to serve as anode liquid;
wherein the voltage applied between the anode plate and the cathode plate is 1-20V direct current;
the composition of the catholyte is as follows: the molar ratio of iodine to soluble iodide is 1:1-1:5, and the iodine is dissolved in pure water to prepare the iodine-containing mass concentration range of 1-50%, and the iodine ion mass concentration range of 1-60%; the mass concentration of the anolyte soluble alkali solution or the soluble oxysalt solution is 0.1-50%;
the two sides of the bipolar membrane are respectively provided with a cationic membrane and an anionic membrane, the anode plate faces the anionic membrane of the bipolar membrane, and the cathode plate faces the cationic membrane of the bipolar membrane; wherein the anionic membrane allows anions to pass through and cations cannot pass through; the cationic membrane may allow cations to pass through and anions may not.
Based on the above synthesis device, the inventors further provide a specific synthesis process:
(1) Putting iodine and soluble iodide into a cathode tank, wherein the molar ratio of the iodine to the soluble iodide is 1:1-1:5, and the mass concentration range of the iodine is 1% -50% and the mass concentration range of the iodide ions is 1% -60% after the iodine and the soluble iodide are mixed with water, so that the electrosynthesis cathode liquid is obtained; the molar ratio of iodine to soluble iodide may be chosen to be greater but uneconomical;
(2) Adding deionized water into a container, slowly adding soluble alkali solid or soluble oxysalt, continuously stirring, adjusting the mass concentration of the solution to be 0.1-50% after the soluble alkali or the soluble oxysalt is completely dissolved, and adding the solution into an anode tank to obtain an electrosynthesis anode solution; the mass concentration of the anolyte can be selected to be larger, but the effect can be poor;
(3) The cathode tank and the anode tank are isolated by a bipolar membrane, and an electrosynthesis power supply is started:
the iodine in the cathode tank is changed into iodine ions under the action of direct current voltage of 1-20V, and the iodine ions are combined with ionized hydrogen ions in water to generate hydroiodic acid;
hydroxide radicals migrate to the anode under the action of direct current voltage of 1-20V in the anode tank to lose electrons to generate oxygen and water;
when the current is constant to gradually become smaller, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, and stopping the reaction after the content of free iodine is reduced to a certain degree, wherein the mass fraction is generally less than 1%; the reaction may be continued until the free iodine content is reduced to 0.1% and then the reaction may be terminated.
The reaction equation for the above reaction process is as follows:
anode ionization equation: 4OH － -4e － ＝O 2 +2H 2 O
Cathode ionization equation: 2I 2 +4e-＝4I-
Between two poles: 4H (4H) 2 O＝4OH-+4H +
General chemical reaction formula: 2I 2 +2H 2 O→4HI+O 2
Under the action of a direct current electric field of the anode plate and the cathode plate, the anode plate is doubleH between cathode and anode film composite layers of polar film 2 O dissociates into H + And OH-and pass through the positive and negative membranes, respectively, as H + And an OH-ion source at the cathode due to I 2 The standard electrode potential of (2) was 0.5345V and the standard electrode potential of hydrogen ion was 0V, indicating I 2 Is more oxidizing than hydrogen ions, thereby I 2 More easily get electrons from the cathode, I 2 Two electrons are obtained at the cathode and become 2 iodide ions, H between the iodide ions and the bipolar membrane composite layer 2 The hydrogen ions dissociated from O are combined into hydrogen iodide, and the hydrogen iodide is dissolved in water to form hydroiodic acid. At the same time, H between the anode and bipolar membrane composite layers 2 The OH-ions dissociated by O migrate to the anode to discharge to generate oxygen and water, and new hydrogen ions and hydroxyl ions are dissociated continuously by the water under the direct current field, so that the hydrogen ions move to the cathode continuously, the hydroxyl ions move to the anode, and iodine continuously obtains electrons from the cathode to become iodide ions, thereby forming current between the cathode and the anode, and the whole reaction can be continuously carried out.
Further, in order to obtain a preparation method which can be industrially applied, the inventor further optimizes the process on the basis of the process, and the following industrialized preparation method is obtained:
(1) Iodine and soluble iodide are put into a catholyte circulation tank according to the mol ratio of 1:1-1:5 and mixed with water to prepare a solution with the iodine mass concentration of 1-50% and the iodine ion mass concentration of 1-60%, namely the electrosynthesis catholyte;
(2) Adding deionized water into a container, slowly adding soluble alkali or soluble oxysalt solid, continuously stirring, adjusting the solution to be a solution with the mass concentration of 0.1-50% after the solid is completely dissolved, and then adding the prepared solution into an anolyte circulation tank;
(3) Respectively starting a cathode tank liquid circulating pump, an anode tank liquid circulating pump and an anode liquid cooling circulating pump, pumping liquid in an anode liquid tank and liquid in a cathode tank into the anode tank and the cathode tank for reaction, and simultaneously keeping the circulation of the cathode liquid and the anode liquid, wherein the cathode liquid continuously circulates between the cathode tank and the cathode liquid circulating tank, so that the concentration uniformity of the cathode liquid can be ensured, and the anode liquid continuously circulates between the anode tank and the anode liquid circulating tank, so that the concentration uniformity of the anode liquid can be ensured;
(4) Starting an electric synthesis power supply, and starting the electric synthesis power supply:
the iodine in the cathode tank is changed into iodine ions under the action of direct current voltage of 1-20V, and the iodine ions are combined with ionized hydrogen ions in water to generate hydroiodic acid;
hydroxide radicals migrate to the anode under the action of direct current voltage of 1-20V in the anode tank to lose electrons to generate oxygen and water;
when the current is constant to gradually become smaller, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, and finishing synthesis after the mass fraction of the free iodine is less than 1%;
(5) The synthesis process can properly release heat, the temperature of materials is increased, the temperature of circulating liquid is controlled between 0 and 70 ℃ through an anolyte cooler, and the damage of high temperature to equipment is prevented;
(6) The synthesis process is completed under normal pressure, an emptying port of the anode system is arranged on the anolyte circulation tank, and generated oxygen is emptied from the emptying port;
(7) After the synthesis is finished, the catholyte is pumped into a dilute hydroiodic acid solution temporary storage tank through a catholyte circulating pump;
(8) Pumping the dilute hydroiodic acid solution into a distillation kettle, starting stirring, starting heating, gradually raising the temperature of the material to 125-140 ℃, collecting the front fraction for recycling in a front fraction tank, and collecting the fraction at 125-130 ℃ to obtain the product hydroiodic acid;
the process is an industrial implementation process, can meet the requirement of large-scale production, and the soluble iodides are used for dissolving iodine in the common process and the industrial production process, wherein the soluble iodides comprise hydriodic acid, sodium iodide, potassium iodide, calcium iodide, lithium iodide, magnesium iodide, zinc iodide, aluminum iodide, ferrous iodide, rubidium iodide, cesium iodide, barium iodide, strontium iodide, titanium tetraiodide, cobalt iodide and a mixture of any of a plurality of the above compounds in any proportion; preference is given to hydroiodic acid, potassium iodide and sodium iodide, and the iodides are cheap and easy to obtain, so that the cost is reduced;
the soluble alkali is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide, strontium hydroxide, calcium hydroxide or a mixture of any of the above materials in any proportion, wherein potassium hydroxide, sodium hydroxide and lithium hydroxide are preferred; the soluble oxysalt comprises sulfate, phosphate, nitrate, carbonate and the like, or a mixture of any two or more of the above.
Further controlling the concentration of the soluble alkali liquor between 2% and 20%;
the electrode synthesis anode is a corrosion-resistant low-oxygen evolution potential electrode, and the adopted electrode synthesis anode is a corrosion-resistant high-hydrogen evolution potential electrode; the anode plate and the cathode plate are made of graphite and titanium or titanium as base materials and are externally plated with corrosion-resistant noble metal coating materials, wherein the noble metal coating comprises ruthenium, rhodium, iridium, platinum, palladium, nickel, tantalum, gold, any noble metal and noble metal mixed coating with any proportion;
on the basis, the cathode plate is preferably a titanium palladium rhodium electrode or a titanium iridium rhodium electrode or a titanium electrode, and the anode plate is preferably a titanium palladium rhodium electrode or a titanium iridium rhodium electrode.
The synthetic voltage is 2-10V; the synthesis temperature is 10-40 ℃.
In order to improve the production efficiency, a plurality of electrosynthesis unit cells in the invention can be connected in series or in parallel, preferably in parallel, so as to provide more productivity.
In summary, the invention provides a brand-new industrial production method of the hydriodic acid, the purity of the hydriodic acid product produced by the method is extremely high, inflammable and explosive objects such as phosphorus are not utilized in the production process, and the synthesis is carried out under normal pressure, so that the safety of the hydriodic acid produced by the method is greatly improved, only oxygen is produced in the production process, and the method has no pollution to the environment, and is a safe, efficient and green synthesis method for the hydriodic acid production.
Drawings
FIG. 1 is a schematic diagram of the structure of the electrosynthesis cell according to the present invention.
The specific embodiment is as follows:
the technical scheme of the invention is not limited to the following specific embodiments, and also comprises appropriate extension according to the content of the specific embodiments.
Example 1
A method suitable for the industrial production of hydroiodic acid comprises the following steps:
a. preparing a catholyte, adding iodine and hydroiodic acid into a catholyte circulation tank according to a molar ratio of 1:1.2, mixing with water, adjusting the mass concentration range of iodine to be 20% -25%, adding 100g of iodine and 106g of 57% concentration hydroiodic acid, and preparing the product after the iodine is completely dissolved.
b. Preparing an anode liquid, adding deionized water into a container, slowly adding potassium hydroxide solid, continuously stirring, preparing 1000g of alkaline solution with the concentration of 5% -6% after potassium hydroxide is completely dissolved, and adding into an anode liquid circulating tank, wherein the anode liquid can be recycled all the time.
c. Starting a catholyte circulation pump and an anolyte circulation pump respectively, controlling the temperature of the anolyte to be between 30 and 40 ℃, starting an electrosynthesis power supply, controlling the voltage of a direct-current power supply to be between 2 and 3V, when the current is constant to gradually decrease, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, after the mass fraction of the free iodine is less than 1%, completing synthesis, and pumping the catholyte into a hydroiodic acid dilute solution temporary storage tank.
d. Pumping the dilute solution of the hydroiodic acid into a distillation kettle, and heating the dilute solution of the hydroiodic acid in the kettle. The temperature of the material is raised to 125-140 ℃, the front cut fraction is collected to be recycled in a front cut tank, the front cut fraction with the temperature of 125-130 ℃ is collected to obtain 251g of product, 166g of front cut fraction with the concentration of 10% of hydroiodic acid and distilled mother liquor are obtained, the total yield of iodine is more than 99%, the content of hydroiodic acid is 57.2%, and the obtained front cut fraction and distilled mother liquor can be used for dissolving iodine when preparing cathode liquor and returning to a production system.
The obtained product indexes are as follows:
| detection item | Detecting a value |
| Content% | 57.2 |
| Burning residues | ≤0.01 |
| Chloride and bromide (in Cl)% | ≤0.002 |
| Free iodine% | ≤0.06 |
| Sulfate% | ＜0.002 |
| Phosphate% | ≤0.030 |
| Iron% | ＜0.0003 |
| Heavy metal (in Pb)% | ＜0.0005 |
| Density of | ≥1.70 |
The electrosynthesis device comprises two reaction chambers separated by a bipolar membrane, wherein a cathode electrode plate and an anode electrode plate are respectively arranged at two sides of the bipolar membrane, one side of the cathode electrode plate is a cathode groove, and the other side of the anode electrode plate is an anode groove; the two sides of the bipolar membrane are respectively provided with a cationic membrane and an anionic membrane, the anode plate faces the anionic membrane of the bipolar membrane, and the cathode plate faces the cationic membrane of the bipolar membrane;
wherein the anionic membrane allows anions to pass through and cations cannot pass through; the cationic membrane may allow cations to pass through and anions may not.
Example 2
A method suitable for the industrial production of hydroiodic acid comprises the following steps:
a. preparing a cathode liquid, adding iodine and potassium iodide into a cathode liquid circulation tank according to a molar ratio of 1:1.2, mixing with water, adjusting the mass concentration range of iodine to be 20% -25%, adding 100g of iodine and 80g of potassium iodide together, and preparing after the iodine is completely dissolved
b. Preparing an anode liquid, adding deionized water into a container, slowly adding sodium hydroxide solid, continuously stirring, preparing 1000g of alkaline solution with the concentration of 7-8% after sodium hydroxide is completely dissolved, and adding into an anode liquid circulating tank, wherein the anode liquid can be recycled all the time.
c. Starting a catholyte circulation pump and an anolyte circulation pump respectively, controlling the temperature of the anolyte to be between 20 and 30 ℃, starting an electrosynthesis power supply, controlling the voltage of a direct-current power supply to be between 3 and 4V, when the current is constant to gradually decrease, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, after the mass fraction of the free iodine is less than 1%, completing synthesis, and pumping the catholyte into a hydroiodic acid dilute solution temporary storage tank.
d. Pumping the dilute solution of the hydroiodic acid into a distillation kettle, and heating the dilute solution of the hydroiodic acid in the kettle. The temperature of the material is raised to 125-140 ℃, the front cut fraction is collected to a front cut fraction tank for recycling, the front cut fraction at 125-130 ℃ is collected to obtain 140g of product, the obtained front cut fraction is combined with distilled mother liquor, the measured iodine content in the solution is 80.9g, the total iodine yield is more than 99% and the hydroiodic acid product content is 57.3%, and the obtained front cut fraction and distilled mother liquor can be used for preparing the cathode liquid to dissolve iodine and return to a production system.
The obtained product indexes are as follows:
| detection item | Detecting a value |
| Content% | 57.3 |
| Burning residues | ≤0.01 |
| Chloride and bromide (in Cl)% | ≤0.002 |
| Free iodine% | ≤0.06 |
| Sulfate% | ＜0.002 |
| Phosphate% | ≤0.030 |
| Iron% | ＜0.0003 |
| Heavy metal (in Pb)% | ＜0.0005 |
| Density of | ≥1.70 |
The electrosynthesis device comprises two reaction chambers separated by a bipolar membrane, wherein a cathode electrode plate and an anode electrode plate are respectively arranged at two sides of the bipolar membrane, one side of the cathode electrode plate is a cathode groove, and the other side of the anode electrode plate is an anode groove; the two sides of the bipolar membrane are respectively provided with a cationic membrane and an anionic membrane, the anode plate faces the anionic membrane of the bipolar membrane, and the cathode plate faces the cationic membrane of the bipolar membrane;
wherein the anionic membrane allows anions to pass through and cations cannot pass through; the cationic membrane may allow cations to pass through and anions may not.
Example 3
A method suitable for the industrial production of hydroiodic acid comprises the following steps:
a. preparing a cathode liquid, adding iodine and sodium iodide into a cathode liquid circulation tank according to a molar ratio of 1:1.3, mixing with water, adjusting the mass concentration range of iodine to be 20% -25%, adding 100g of iodine and 77g of sodium iodide, and preparing after the iodine is completely dissolved
b. Preparing an anode liquid, adding deionized water into a container, slowly adding sodium sulfate solid, continuously stirring, preparing 1000g of solution with the concentration of 5-6% after sodium sulfate is completely dissolved, and adding into an anode liquid circulating tank, wherein the anode liquid can be recycled all the time.
c. Starting a catholyte circulation pump and an anolyte circulation pump respectively, controlling the temperature of the anolyte to be between 20 and 30 ℃, starting an electrosynthesis power supply, controlling the voltage of a direct-current power supply to be between 3 and 4V, when the current is constant to gradually decrease, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, after the mass fraction of the free iodine is less than 1%, completing synthesis, and pumping the catholyte into a hydroiodic acid dilute solution temporary storage tank.
d. Pumping the dilute solution of the hydroiodic acid into a distillation kettle, and heating the dilute solution of the hydroiodic acid in the kettle. The temperature of the material is raised to 125-140 ℃, the front cut fraction is collected to be recycled in a front cut tank, the front cut fraction at 125-130 ℃ is collected to obtain 135g of product, the obtained front cut fraction is combined with distilled mother liquor, the iodine content in the solution is 87.1g, the total yield of iodine is more than 99% in terms of iodine, the content of hydroiodic acid product is 57.1%, and the obtained front cut fraction and distilled mother liquor can be used for preparing the cathode liquid to dissolve iodine and return to a production system.
The obtained product indexes are as follows:
| detection item | Detecting a value |
| Content% | 57.1 |
| Burning residues | ≤0.01 |
| Chloride and bromide (in Cl)% | ≤0.002 |
| Free iodine% | ≤0.06 |
| Sulfate% | ＜0.002 |
| Phosphate% | ≤0.030 |
| Iron% | ＜0.0003 |
| Heavy metal (in Pb)% | ＜0.0005 |
| Density of | ≥1.70 |
The electrosynthesis device comprises two reaction chambers separated by a bipolar membrane, wherein a cathode electrode plate and an anode electrode plate are respectively arranged at two sides of the bipolar membrane, one side of the cathode electrode plate is a cathode groove, and the other side of the anode electrode plate is an anode groove; the two sides of the bipolar membrane are respectively provided with a cationic membrane and an anionic membrane, the anode plate faces the anionic membrane of the bipolar membrane, and the cathode plate faces the cationic membrane of the bipolar membrane;
wherein the anionic membrane allows anions to pass through and cations cannot pass through; the cationic membrane may allow cations to pass through and anions may not.
Claims (11)
1. An industrial production method of hydroiodic acid is characterized in that an electrochemical synthesis method is adopted, and an electrochemical synthesis unit device used comprises:
(1) Two reaction chambers separated by a bipolar membrane;
(2) The cathode electrode plate and the anode electrode plate are respectively arranged at two sides of the bipolar membrane; the cathode plate is provided with a cathode groove at one side, and a catholyte is placed in the cathode groove, wherein the catholyte consists of an aqueous solution containing iodine and soluble iodide; the anode plate is provided with an anode groove at one side, and a soluble alkali solution or a soluble oxysalt solution is put in the anode groove to serve as anode liquid;
wherein the voltage applied between the anode plate and the cathode plate is 1-20V direct current;
the composition of the catholyte is as follows: the molar ratio of iodine to soluble iodide is 1:1-1:5, and the iodine is dissolved in pure water to prepare the iodine-containing mass concentration range of 1-50%, and the iodine ion mass concentration range of 1-60%; the mass concentration of the anolyte soluble alkali solution or the soluble oxysalt solution is 0.1-50%;
after the voltage is applied to the electrode plate, the following reaction occurs:
anode ionization equation: 4OH － - 4e － =O 2 ＋2H 2 O
Cathode ionization equation: 2I 2 + 4e - = 4I -
Between two poles: 4H (4H) 2 O = 4OH - + 4H +
General chemical reaction formula: 2I 2 + 2H 2 O → 4HI + O 2 ，
When the current is constant to gradually become smaller, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, and stopping the reaction after the mass fraction of the free iodine is less than 1%.
2. The industrial production method of hydroiodic acid according to claim 1, characterized in that: the method comprises the following steps:
(1) Iodine and soluble iodide are put into a catholyte circulation tank according to the mol ratio of 1:1-1:5 and mixed with water to prepare a solution with the iodine mass concentration of 1-50% and the iodine ion mass concentration of 1-60%, namely the electrosynthesis catholyte;
(2) Adding deionized water into a container, slowly adding soluble alkali or soluble oxysalt solid, continuously stirring, adjusting the mass concentration of the solution to be 0.1-50% after the soluble alkali or soluble oxysalt is completely dissolved, and then adding the prepared soluble alkali or soluble oxysalt solution into an anode solution circulation tank;
(3) Respectively starting a cathode tank liquid circulating pump, an anode tank liquid circulating pump and an anode liquid cooling circulating pump, pumping liquid in an anode liquid tank and liquid in a cathode tank into the anode tank and the cathode tank for reaction, and simultaneously keeping the circulation of the cathode liquid and the anode liquid, wherein the cathode liquid continuously circulates between the cathode tank and the cathode liquid circulating tank, so that the concentration uniformity of the cathode liquid can be ensured, and the anode liquid continuously circulates between the anode tank and the anode liquid circulating tank, so that the concentration uniformity of the anode liquid can be ensured;
(4) Starting an electrosynthesis power supply:
the iodine in the cathode tank is changed into iodine ions under the action of direct current voltage of 1-20V, and the iodine ions are combined with ionized hydrogen ions in water to generate hydroiodic acid;
hydroxide radicals migrate to the anode under the action of direct current voltage of 1-20V in the anode tank to lose electrons to generate oxygen and water;
when the current is constant to gradually become smaller, extracting the catholyte to observe that the color is changed from black to light red, detecting the content of free iodine in the catholyte, and finishing synthesis after the mass fraction of the free iodine is less than 1%;
(5) The synthesis process can properly release heat, the temperature of materials is increased, the temperature of circulating liquid is controlled between 0 and 70 ℃ through an anolyte cooler, and the damage of high temperature to equipment is prevented;
(6) The synthesis process is completed under normal pressure, an emptying port of the anode system is arranged on the anolyte circulation tank, and generated oxygen is emptied from the emptying port;
(7) After the synthesis is finished, the catholyte is pumped into a dilute hydroiodic acid solution temporary storage tank through a catholyte circulating pump;
(8) Pumping the dilute hydroiodic acid solution into a distillation kettle, starting stirring, starting heating, gradually raising the temperature of the material to 125-140 ℃, collecting the front fraction for recycling in a front fraction tank, and collecting the fraction at 125-130 ℃ to obtain the product hydroiodic acid.
3. The industrial production method of hydroiodic acid according to claim 1 or 2, characterized in that: the soluble iodide is selected from one or more of hydriodic acid, sodium iodide, potassium iodide, calcium iodide, lithium iodide, magnesium iodide, zinc iodide, aluminum iodide, ferrous iodide, rubidium iodide, cesium iodide, barium iodide, strontium iodide, titanium tetraiodide and cobalt iodide, and the mixture of any two or more of them in any proportion.
4. The industrial production method of hydroiodic acid according to claim 3, characterized in that: the soluble iodide is preferably one or more selected from hydroiodic acid, potassium iodide and sodium iodide.
5. The industrial production method of hydroiodic acid according to claim 1 or 2, characterized in that: the soluble alkali is selected from one or a mixture of any of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, barium hydroxide, strontium hydroxide and calcium hydroxide in any proportion; the soluble oxysalt is selected from one or a mixture of any of soluble sulfate, nitrate, phosphate, carbonate and other inorganic oxysalts in any proportion.
6. The industrial production method of hydroiodic acid according to claim 5, characterized in that: the soluble alkali is preferably potassium hydroxide or sodium hydroxide; the concentration is controlled between 1% and 20%.
7. The industrial production method of hydroiodic acid according to claim 1 or 2, characterized in that: the electrosynthesis anode is a corrosion-resistant low oxygen evolution potential electrode, and the adopted electrosynthesis anode is a corrosion-resistant high hydrogen evolution potential electrode; the anode plate and the cathode plate are made of graphite or titanium as a base material and are externally plated with corrosion-resistant noble metal coating, wherein the noble metal coating comprises ruthenium, rhodium, iridium, platinum, palladium, nickel, tantalum, gold, any noble metal and noble metal mixed coating with any proportion.
8. The industrial production method of hydroiodic acid according to claim 1 or 2, characterized in that: the cathode is a titanium palladium-rhodium plating electrode or a titanium iridium-rhodium plating electrode or a titanium electrode, and the anode is a titanium palladium-rhodium plating electrode or a titanium iridium-rhodium plating electrode.
9. The industrial production method of hydroiodic acid according to claim 1 or 2, characterized in that: the synthetic direct-current voltage is 2-10V; the synthesis temperature is 10-40 ℃.
10. The production method of hydroiodic acid according to claim 1 or 2, characterized in that: in the synthesis process, a plurality of electrosynthesis unit cells are connected in series or in parallel.
11. The method for producing hydroiodic acid according to claim 10, characterized in that: in the synthesis process, a plurality of electrosynthesis unit cells are connected in parallel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810780327.3A CN110724968B (en) | 2018-07-16 | 2018-07-16 | Industrial production method of hydroiodic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810780327.3A CN110724968B (en) | 2018-07-16 | 2018-07-16 | Industrial production method of hydroiodic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110724968A CN110724968A (en) | 2020-01-24 |
| CN110724968B true CN110724968B (en) | 2023-06-23 |
Family
ID=69216967
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810780327.3A Active CN110724968B (en) | 2018-07-16 | 2018-07-16 | Industrial production method of hydroiodic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110724968B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111394746B (en) * | 2020-04-10 | 2021-06-08 | 山东博苑医药化学股份有限公司 | Electrochemical co-production method of potassium iodate and hydroiodic acid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4053376A (en) * | 1976-10-27 | 1977-10-11 | Ppg Industries, Inc. | Electrolytic production of hydrogen iodide |
| US5520793A (en) * | 1995-04-03 | 1996-05-28 | Benham Electrosynthesis Company, Inc. | Methods of producing hydrogen iodide electrochemically |
| JP3521163B2 (en) * | 1995-08-18 | 2004-04-19 | ペルメレック電極株式会社 | Method for producing hydroiodic acid |
-
2018
- 2018-07-16 CN CN201810780327.3A patent/CN110724968B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Kim Taeeon et al,.Effect of Iodine-coated Bipolar Plates on the Performance of a Polymer Exchange Membrane (PEM) Fuel Cell.Transactions of the Korean hydrogen and new energy society.2013,第24卷(第1期),61-69. * |
| Stanisław Koter et al..A new model for characterization of bipolar membrane electrodialysis of brine.Desalination.2006,第198卷(第1期),111-123. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110724968A (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0532188A2 (en) | Electrochemical process | |
| US20080003507A1 (en) | Formulation Of Electrolyte Solutions For Electrochemical Chlorine Dioxide Generators | |
| US3523068A (en) | Process for electrolytic preparation of quaternary ammonium compounds | |
| CN107709621A (en) | Utilize the water treatment system for having buck electrolysis unit and alkaline fuel cell | |
| CN110656343A (en) | Method for preparing double-alkali co-production high-purity gypsum from mirabilite and limestone by utilizing PCET reaction | |
| CN102828198A (en) | Method for preparing high-purity quaternary ammonium hydroxide by electrolyzing organic ammonium salt with perfluorinated ion exchange membrane in chlor-alkali | |
| CN110724968B (en) | Industrial production method of hydroiodic acid | |
| EP3473750A1 (en) | Electrolysis system and electrolysis method using same | |
| CN105063654A (en) | Method for preparing methanesulfonic acid and sodium hydroxide by utilizing sodium methanesulfonate | |
| CN110438519B (en) | Three-electrolytic-tank chlor-alkali electrolysis preparation system and chlor-alkali preparation method | |
| CN102021600A (en) | Method and device for producing potassium iodate through oxygen cathode non-diaphragm electrolysis | |
| CN110724967A (en) | Production method of hydroiodic acid | |
| DE2240731C3 (en) | Process for the production of glyoxylic acid | |
| US4634506A (en) | Process for preparing olefin oxides | |
| CN113666367B (en) | Electrolytic tank for preparing graphite intercalation and preparation method of graphite intercalation | |
| CN103663563B (en) | Preparation method of potassium ferrate | |
| CN112028025B (en) | Green production process of insoluble iodate | |
| US20230053763A1 (en) | Method for preparing periodates | |
| DE1244749B (en) | Method and device for the immediate and simultaneous production of inorganic alkali salts and chlorine gas | |
| US1309214A (en) | Hugh k | |
| CN110670084A (en) | Method for preparing salt by adopting electrolysis method | |
| US5578182A (en) | Electrolytic production of hypophosphorous acid | |
| US4402805A (en) | Electrochemical process to prepare p-hydroxymethylbenzoic acid with a low level of 4-CBA | |
| CN110724969A (en) | Industrial production method of soluble iodide | |
| JPS61231189A (en) | Production of amino alcohol |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |