CN112725825A - Method for preparing glyoxylic acid by electrolyzing oxalic acid - Google Patents
Method for preparing glyoxylic acid by electrolyzing oxalic acid Download PDFInfo
- Publication number
- CN112725825A CN112725825A CN202011352842.5A CN202011352842A CN112725825A CN 112725825 A CN112725825 A CN 112725825A CN 202011352842 A CN202011352842 A CN 202011352842A CN 112725825 A CN112725825 A CN 112725825A
- Authority
- CN
- China
- Prior art keywords
- storage tank
- cathode
- tank
- acid
- reaction
- 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.)
- Pending
Links
Images
Abstract
The invention discloses a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolytic cell, an anode storage tank, a desalted water pump, a cathode feed pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolytic cell, the desalted water storage tank is connected with the additive dissolving tank and the cathode storage tank by the desalted water pump, and the additive dissolving tank is connected with the cathode storage tank by the desalted water pump. In the electrolytic process, the feeding temperature of the electrolyte is controlled, the discharged material of the electrolytic cell is firstly pumped back to the catholyte buffer tank to perform the first mixed heat exchange with other feed liquid, so that the load of subsequent heat exchange can be reduced, the amount of oxalic acid in the feed liquid can be supplemented, the reaction rate can be maintained, and the discharged material is pumped back to the electrolytic cell to perform the circulating reaction after the second heat exchange.
Description
Technical Field
The invention belongs to the technical field of organic electrolysis, and particularly relates to a method for preparing glyoxylic acid by electrolyzing oxalic acid.
Background
Glyoxylic acid is an important chemical raw material and an intermediate, and is widely applied to the fields of medicines, pesticides, spices, paper making, food additives, biochemistry and the like. At present, the method is mainly used for producing broad-spectrum antibiotics amoxicillin, perfume vanillin, antihypertensive drug atenolol, cosmetic additive allantoin, high value-added aromatic aldehyde and pesticide intermediates. The industrial production method of the glyoxylic acid mainly comprises a glyoxal nitric acid oxidation method, an oxalic acid electrolytic reduction method and a maleic anhydride ozone oxidation method, and the industrial product is usually 40% or 50% glyoxylic acid aqueous solution. Because the oxalic acid electrolytic reduction method has low product concentration and high production cost, and is difficult to produce on a large scale, the glyoxalic acid is mainly produced by a glyoxal nitric acid oxidation method in the industry at present.
In the process of producing glyoxylic acid by a glyoxal nitric acid oxidation method, 0.25-0.30 ton of oxalic acid is produced as a byproduct for producing 1 ton of 40% glyoxylic acid aqueous solution. The by-product oxalic acid is powdery in appearance and contains a small amount of glyoxylic acid impurities, and recrystallization is needed to reach the national standard of industrial oxalic acid. The oxalic acid as a byproduct of glyoxylic acid production enterprises is generally treated at low price and has low economic value, and enterprises hope to adopt simpler equipment to electrolyze and reduce the oxalic acid as the byproduct into dilute solution of glyoxylic acid so as to improve the yield of glyoxylic acid and the economic benefit of the production process.
The electrolysis methods are classified into a diaphragm electrolysis method and a diaphragm-free electrolysis method. In the process of producing glyoxylic acid by a diaphragm electrolysis method, a diaphragm is easy to break, the electrolysis power consumption is high, the electrolysis process is unstable, and a method for preparing glyoxylic acid by electrolytic reduction of an oxalic acid cathode is described in U.S. patent 469226, wherein the method indicates that whether intermittent or continuous production is adopted, the molar concentration of oxalic acid in a feed liquid is preferably kept at 0.7 +/-0.1M, which is equivalent to the mass concentration of about 55-80 g/L of the feed liquid. However, neither batch nor continuous production is described or illustrated in any way; chinese patent CN1322860A also describes a method for preparing glyoxylic acid by cathodic electrolysis reduction of oxalic acid. The method adopts intermittent production, oxalic acid solution is stored in a storage tank, oxalic acid feed liquid is continuously reacted and circulated in one storage tank and an electrolytic tank until the mass concentration of glyoxylic acid in the feed liquid reaches 6-10 wt%, and then the feed liquid is pumped into a subsequent product separation section. The above steps are then repeated. However, the method is not continuous in production and is not suitable for industrial production.
Therefore, it is necessary to develop a method for preparing glyoxylic acid by electrolyzing oxalic acid to solve the problems.
Disclosure of Invention
In view of the above problems, the present invention provides a method for preparing glyoxylic acid by electrolyzing oxalic acid, so as to solve the problems presented in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a method for preparing glyoxylic acid by oxalic acid electrolysis comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolytic cell, an anode storage tank, a desalted water pump, a cathode feed pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolytic cell;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
Furthermore, the raw materials for preparing the glyoxylic acid are oxalic acid solution and ammonium bromide solution, and a plate-and-frame filter-press diaphragm-free electrolytic cell with a simple structure is adopted.
Further, the process of preparing glyoxylic acid comprises a cathode reaction and an anode reaction, wherein the cathode reaction comprises a main reaction and a side reaction, and the specific flow comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 15 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte enters an electrolytic bath from a catholyte buffer tank and an anode storage tank respectively at the flow rate of 0.55-1.1m/s and anolyte at the speed of 1-2.2m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, and then enters the electrolytic bath again through heat exchange, and the steps are repeated in such a way until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration;
s5: opening a discharge valve to allow a part of electrolyte to enter a subsequent refining section; and simultaneously, the feeding valve is opened again, so that the fresh feed liquid enters the cathode liquid buffer tank at a certain speed.
Further, the cell voltage in the electrolytic cell in the step S4 is set at any section of 4.3-15.5V.
The invention has the technical effects and advantages that:
1. in the electrolytic process, the feeding temperature of the electrolyte is controlled, the discharged material of the electrolytic cell is firstly pumped back to the catholyte buffer tank to perform the first mixed heat exchange with other feed liquid, so that the load of subsequent heat exchange can be reduced, the amount of oxalic acid in the feed liquid can be supplemented, the reaction rate can be maintained, and the discharged material is pumped back to the electrolytic cell to perform the circulating reaction after the second heat exchange.
2. The electrolytic cell is electrolyzed by maintaining high current efficiency, and the current density is controlled, so that the electrolyte is continuously circulated and electrolyzed until the concentration of the glyoxylic acid in the electrolyte reaches an optimal value, a part of the electrolyte is conveyed to a downstream refining section, and meanwhile, an equal amount of fresh oxalic acid at the upstream is continuously pumped into a cathode liquid storage tank from the cathode storage tank, so that the dynamic balance is realized, the concentration of the oxalic acid in the electrolyte is maintained, and simultaneously, the glyoxylic acid discharged by the electrolytic cell is maintained at a high concentration so as to reduce the refined separation load.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and it is also possible for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 shows a flow chart of an embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1.1m/s and anolyte at the speed of 1.1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, then enters the electrolytic cell again after heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 5.5-9.1V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example two:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1.1m/s and anolyte at the speed of 1.1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, then enters the electrolytic cell again after heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 5.6-8.7V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example three:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 15 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1.1m/s and anolyte at the speed of 1.1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, then enters the electrolytic cell again after heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 4.3-5.1V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example four:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 0.55m/s and anolyte at the speed of 1.1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, then enters the electrolytic cell again after heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 4.6-5.7V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example five:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1.1m/s and anolyte at the speed of 2.2m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, then enters the electrolytic cell again after heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 4.1-4.4V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example six:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1m/s and anolyte at the rate of 1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank and then enters the electrolytic cell again through heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 7.6-15.5V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example seven:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1m/s and anolyte at the rate of 1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank and then enters the electrolytic cell again through heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 6.3-10.3V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example eight:
the invention provides a method for preparing glyoxylic acid by oxalic acid electrolysis, which comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolyzer, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, wherein an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolyzer;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
As a specific embodiment of the invention, the process for preparing glyoxylic acid is divided into a cathode reaction and an anode reaction, wherein the cathode reaction is divided into a main reaction and a side reaction, and the specific process comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
the method for preparing glyoxylic acid by electrolyzing oxalic acid comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 12-20 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte respectively enters an electrolytic cell from a catholyte buffer tank and an anode storage tank at the flow rate of 1m/s and anolyte at the rate of 1m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank and then enters the electrolytic cell again through heat exchange, and the process is circulated until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration, wherein the voltage of the electrolytic cell is 6.0-8.0V in the electrolytic process;
s5: and opening a discharge valve to allow a part of electrolyte to enter a subsequent refinement working section, and simultaneously, reopening a feed valve to allow fresh feed liquid to enter a cathode liquid buffer tank at a certain speed.
Example nine:
data study: the results of comparing the values of the electrolysis processes of examples 1-8 with the data of U.S. Pat. No. 469226 and Chinese patent No. 1322860A are shown in the following table:
| conditions of example | 1 | 2 | 3 | 4 | 5 | 6 | 7 | 8 | United states patent 469226 | Chinese patent 1322860A |
| Mode of electrolysis | Constant current | Constant current | Constant current | Constant current | Constant current | Constant current | Constant current | Constant current | Constant current | Constant current |
| Cell voltage V | 5.5-9.1 | 5.6-8.7 | 4.3-5.1 | 4.6-5.7 | 4.1-4.4 | 7.6-15.5 | 6.3-10.3 | 6.0-8.0 | 8 | 5 |
| Operating current A | 34 | 34 | 34 | 34 | 34 | 34 | 34 | 34 | 34 | 34 |
| Electrolysis temperature C | 12-20 | 12-20 | 15 | 12-20 | 12-20 | 12-20 | 12-20 | 12-20 | 20 | 10 |
| Cathode liquid flow velocity m/s | 1.1 | 1.1 | 1.1 | 0.55 | 1.1 | 1 | 1 | 1 | 1 | 1 |
| Catholyte oxalic acid concentration% wt | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 | 5-8 |
| Volume L of catholyte | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Volume L of anolyte | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 | 4 |
| Anolyte sulfuric acid concentration% wt | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 | 20 |
| Flow velocity m/s of anolyte | 1.1 | 1.1 | 1.1 | 1.1 | 2.2 | 1 | 1 | 1 | 1 | 1 |
| Electrolysis time h | 7 | 7 | 7 | 7 | 7 | 7 | 8 | 5 | 36 | 7 |
| Current efficiency% | 66.9 | 78.2 | 76.8 | 82.3 | 77.1 | 65.2 | 54.3 | 71.4 | 61.6 | 64.1 |
| Glyoxylic acid concentration g/L | 54.9 | 64.2 | 63.1 | 62.2 | 58.3 | 53.5 | 50.9 | 41.9 | 53.1 | 48.7 |
| The power consumption kwh/kg of glyoxylic acid | 7.8 | 5.5 | 4.5 | 4.8 | 19.0 | 9.8 | 10.5 | 7.1 | 22.5 | 2.3 |
And (4) conclusion: in the electrolytic process, the feeding temperature of the electrolyte is controlled, the discharged material of the electrolytic cell is firstly pumped back to the catholyte buffer tank to perform first mixed heat exchange with other feed liquid, so that the load of subsequent heat exchange can be reduced, the amount of oxalic acid in the feed liquid can be supplemented, the reaction rate can be maintained, and the discharged material is pumped back to the electrolytic cell to perform circular reaction after second heat exchange; and the electrolysis is carried out under the higher current efficiency by maintaining the electrolysis, the current density is controlled, so that the electrolyte is continuously circulated and electrolyzed, when the concentration of the glyoxylic acid in the electrolyte reaches the optimal value, a part of the electrolyte is conveyed to a downstream refining workshop section, and meanwhile, the same amount of fresh oxalic acid at the upstream continuously flows into a cathode liquid storage tank from the cathode storage tank, the dynamic balance is realized, the concentration of the oxalic acid in the electrolyte is maintained, and simultaneously, the higher concentration of the glyoxylic acid discharged from the electrolytic tank is maintained so as to reduce the refined separation load.
Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments can still be modified, or some technical features of the foregoing embodiments can be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A method for preparing glyoxylic acid by oxalic acid electrolysis comprises a desalted water storage tank, a cathode storage tank, an ionic membrane electrolytic cell, an anode storage tank, a desalted water pump, a cathode feeding pump and an anode circulating pump, and is characterized in that: an additive dissolving tank is arranged on one side of the desalted water storage tank, and a catholyte buffer tank is arranged between the cathode storage tank and the ionic membrane electrolytic cell;
the desalting water storage tank is connected with the additive dissolving tank and the cathode storage tank through a desalting water pump, the additive dissolving tank is connected with the cathode storage tank through the desalting water pump, the cathode storage tank is connected with the catholyte buffer tank through a cathode feeding pump, the catholyte buffer tank is connected with the negative end of the ionic membrane electrolytic tank through the cathode feeding pump, and the positive end of the ionic membrane electrolytic tank is connected with the positive storage tank through a positive circulating pump.
2. The method for preparing glyoxylic acid by electrolysis of oxalic acid according to claim 1, wherein the method comprises the following steps: the raw materials for preparing the glyoxylic acid are oxalic acid solution and ammonium bromide solution, and a plate-and-frame filter-press diaphragm-free electrolytic cell with a simple structure is adopted.
3. The method for preparing glyoxylic acid by electrolysis of oxalic acid according to claim 1, wherein the method comprises the following steps: the process for preparing the glyoxylic acid comprises a cathode reaction and an anode reaction, wherein the cathode reaction comprises a main reaction and a side reaction, and the specific flow comprises the following steps:
the cathode main reaction is that oxalic acid is hydrogenated to obtain electrons which are reduced to glyoxylic acid (2);
the side reaction is that hydrogen ions are reduced to generate hydrogen (3), and the generated glyoxylic acid can be continuously reduced to glycolic acid (4);
the anode region is diluted acid, such as diluted solution of common strong acid such as phosphoric acid, sulfuric acid or hydrochloric acid, the anode reaction is electrolyzed water (1), a small amount of oxygen is generated, electrons are released to form a loop, ionized hydrogen ions enter the cathode region through an ion membrane, and the specific reaction equation is as follows:
anode:
（1）
cathode:
（2）
4. a method for the electrolytic production of glyoxylic acid from oxalic acid according to claims 1 to 3, characterized in that: the method comprises the following steps:
s1: firstly, desalting water is subjected to heat exchange, then the desalting water is pumped into a desalting water storage tank at a fixed temperature of 15 ℃, and then the desalting water is respectively pumped into an additive storage tank and a cathode storage tank;
s2: dissolving the desalted water and the solid quaternary ammonium salt which are discharged from the cathode storage tank into an additive storage tank according to a certain mass ratio, and uniformly stirring to prepare 10-50 wt% of additive concentrated solution;
s3: uniformly stirring solid oxalic acid, additive concentrated solution and desalted water in a cathode storage tank according to a certain proportion, pumping a certain amount of mixed solution into a cathode buffer tank, and closing cathode feeding;
s4: after catholyte in electrolyte enters an electrolytic bath from a catholyte buffer tank and an anode storage tank respectively at the flow rate of 0.55-1.1m/s and anolyte at the speed of 1-2.2m/s for reaction, the catholyte returns to the catholyte buffer tank, the anolyte returns to the anode storage tank, and then enters the electrolytic bath again through heat exchange, and the steps are repeated in such a way until the concentration of glyoxylic acid in the electrolyte reaches the ideal concentration;
s5: opening a discharge valve to allow a part of electrolyte to enter a subsequent refining section; and simultaneously, the feeding valve is opened again, so that the fresh feed liquid enters the cathode liquid buffer tank at a certain speed.
5. The method for preparing glyoxylic acid by electrolysis of oxalic acid according to claim 4, wherein the reaction is carried out by the following steps: the cell voltage in the electrolytic cell in the step S4 is set at any section of 4.3-15.5V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011352842.5A CN112725825A (en) | 2020-11-27 | 2020-11-27 | Method for preparing glyoxylic acid by electrolyzing oxalic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011352842.5A CN112725825A (en) | 2020-11-27 | 2020-11-27 | Method for preparing glyoxylic acid by electrolyzing oxalic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112725825A true CN112725825A (en) | 2021-04-30 |
Family
ID=75597841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011352842.5A Pending CN112725825A (en) | 2020-11-27 | 2020-11-27 | Method for preparing glyoxylic acid by electrolyzing oxalic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112725825A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114016059A (en) * | 2021-11-15 | 2022-02-08 | 东华工程科技股份有限公司 | Method for continuously preparing glyoxylic acid by oxalic acid electrolysis |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064111A (en) * | 1991-04-20 | 1992-09-02 | 张家口市宣化化工厂 | Bipolar chamber paired electrolysis method is produced oxoethanoic acid |
| CN1281063A (en) * | 2000-04-04 | 2001-01-24 | 华东理工大学 | Process for preparing glyoxylic acid by electrolytic reduction of oxalic acid |
| CN1322860A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Oxalic acid electroreduction process of preparing glyoxalic acid |
| CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
| EP1263072A1 (en) * | 2001-05-30 | 2002-12-04 | Casale Chemicals SA | Method and apparatus for the storage and redistribution of electrical energy |
| WO2013082492A1 (en) * | 2011-11-30 | 2013-06-06 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
| CN111850597A (en) * | 2020-06-15 | 2020-10-30 | 中船重工（邯郸）派瑞特种气体有限公司 | Electrochemical fluorination external circulation electrolysis system |
-
2020
- 2020-11-27 CN CN202011352842.5A patent/CN112725825A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064111A (en) * | 1991-04-20 | 1992-09-02 | 张家口市宣化化工厂 | Bipolar chamber paired electrolysis method is produced oxoethanoic acid |
| CN1281063A (en) * | 2000-04-04 | 2001-01-24 | 华东理工大学 | Process for preparing glyoxylic acid by electrolytic reduction of oxalic acid |
| CN1322860A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Oxalic acid electroreduction process of preparing glyoxalic acid |
| CN1322859A (en) * | 2001-04-17 | 2001-11-21 | 华东理工大学 | Paired electrolysis procss of preparing glyoxalic acid |
| EP1263072A1 (en) * | 2001-05-30 | 2002-12-04 | Casale Chemicals SA | Method and apparatus for the storage and redistribution of electrical energy |
| WO2013082492A1 (en) * | 2011-11-30 | 2013-06-06 | Liquid Light, Inc. | Electrochemical production of butanol from carbon dioxide and water |
| CN111850597A (en) * | 2020-06-15 | 2020-10-30 | 中船重工（邯郸）派瑞特种气体有限公司 | Electrochemical fluorination external circulation electrolysis system |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114016059A (en) * | 2021-11-15 | 2022-02-08 | 东华工程科技股份有限公司 | Method for continuously preparing glyoxylic acid by oxalic acid electrolysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4456510A (en) | Process for manufacturing chlorine dioxide | |
| JP6368374B2 (en) | Method and system for preparing lithium hydroxide | |
| EP0544686B1 (en) | Chlorine dioxide generation from chloric acid | |
| US6527940B1 (en) | Production method of acid water and alkaline water | |
| EP0532188A2 (en) | Electrochemical process | |
| CN205151853U (en) | Electrolysis trough that contains salt waste water and retrieve acid -base is simultaneously handled to two units negative pole altogether | |
| CN105329988A (en) | Electrolytic bath for treating high-salt industrial waste water by combining Fenton method with bipolar membrane technology | |
| CN105154910A (en) | Process for producing alkali | |
| CN102839389B (en) | Novel production method of electro-depositing and refining metal chloride by membrane process | |
| CN112725825A (en) | Method for preparing glyoxylic acid by electrolyzing oxalic acid | |
| US3974051A (en) | Production of hypochlorite from impure saline solutions | |
| CN105293642A (en) | Multi-electrode multi-diaphragm electrolytic cell for treating high-salinity industrial wastewater | |
| CN205204884U (en) | Handle many diaphragm electrolysis of multi -electrode groove of high salt industrial waste water | |
| US5466347A (en) | Method for electrolyzing aqueous solution of alkali chloride | |
| CN102828205A (en) | Novel metal electro-deposition refining technology | |
| SU1720495A3 (en) | Method of reducing iron (iii) ions | |
| EP0532535B1 (en) | Electrochemical production of acid chlorate solutions | |
| CN113481521B (en) | Continuous chlor-alkali industrial electrolysis alkali preparation device and method | |
| JPH05179475A (en) | Production of hypochlorite | |
| JP2000005757A (en) | Economical production of electrolytic sterilizing water | |
| CN113388848A (en) | Production method for preparing hypochlorous acid solution by electrolyzing salt | |
| CN111676486A (en) | Sodium hypochlorite production process and device for electrolyzing low-concentration brine by using membrane-free method | |
| CN105271481A (en) | Electrolytic cell for treating salt-bearing wastewater with double-unit common cathode while recycling acid and alkali | |
| CN114016059B (en) | Method for continuously preparing glyoxylic acid by oxalic acid electrolysis | |
| US5256261A (en) | Membrane cell operation |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210430 |