CN113755860A - Process for producing bromine by electrolyzing hydrobromic acid - Google Patents
Process for producing bromine by electrolyzing hydrobromic acid Download PDFInfo
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- CN113755860A CN113755860A CN202111154861.1A CN202111154861A CN113755860A CN 113755860 A CN113755860 A CN 113755860A CN 202111154861 A CN202111154861 A CN 202111154861A CN 113755860 A CN113755860 A CN 113755860A
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- bromine
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- hydrobromic acid
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 229
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 228
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 228
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 238000010025 steaming Methods 0.000 claims abstract description 56
- 239000007788 liquid Substances 0.000 claims abstract description 49
- JGJLWPGRMCADHB-UHFFFAOYSA-N hypobromite Inorganic materials Br[O-] JGJLWPGRMCADHB-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000000926 separation method Methods 0.000 claims abstract description 38
- BSKZDJXVMPWPRA-UHFFFAOYSA-N O.[Br] Chemical compound O.[Br] BSKZDJXVMPWPRA-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 19
- 230000005484 gravity Effects 0.000 claims abstract description 9
- 238000012856 packing Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 60
- 238000005406 washing Methods 0.000 claims description 54
- 229910052739 hydrogen Inorganic materials 0.000 claims description 47
- 239000001257 hydrogen Substances 0.000 claims description 47
- 238000001704 evaporation Methods 0.000 claims description 46
- 230000008020 evaporation Effects 0.000 claims description 46
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 34
- 238000010521 absorption reaction Methods 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 24
- 238000004821 distillation Methods 0.000 claims description 23
- 238000005192 partition Methods 0.000 claims description 17
- 125000006850 spacer group Chemical group 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 9
- 239000010936 titanium Substances 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000000576 coating method Methods 0.000 claims description 7
- 229910052755 nonmetal Inorganic materials 0.000 claims description 6
- 238000005086 pumping Methods 0.000 claims description 5
- 230000000149 penetrating effect Effects 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 abstract description 18
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052801 chlorine Inorganic materials 0.000 abstract description 7
- 239000000460 chlorine Substances 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000006378 damage Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 description 8
- 238000005893 bromination reaction Methods 0.000 description 7
- 239000000945 filler Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- -1 particularly Chemical compound 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
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Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/09—Bromine; Hydrogen bromide
- C01B7/096—Bromine
-
- 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
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- C25B1/50—Processes
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
- C25B11/063—Valve metal, e.g. titanium
-
- 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
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
- C25B11/081—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound the element being a noble metal
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- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/60—Constructional parts of cells
- C25B9/65—Means for supplying current; Electrode connections; Electric inter-cell connections
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a process method for producing bromine by electrolyzing hydrobromic acid, which is characterized in that hydrobromic acid solution is pumped into the bottom of an electrolytic tank according to a certain flow rate, mixed liquor obtained by electrolysis passes through a packing layer after being sprayed in a bromine steaming tower and is heated by steam from bottom to top by virtue of gravity, bromine in the mixed liquor is evaporated in the bromine steaming tower and enters a bromine condenser from the top of the bromine steaming tower after being mixed with partial water vapor, and in the bromine condenser, bromine vapor and water vapor are condensed into liquid to form a mixture of water and bromine, and then the mixture enters a bromine-water separation bottle for separation, so that bromine is obtained. The whole process does not need to add chlorine with larger potential safety hazard as a raw material, reduces the potential safety hazard in the storage and use processes of the chlorine, does not produce acidic wastewater, does not need subsequent treatment, fully utilizes resources, does not damage the environment, better meets the requirement of environmental protection, and improves the economic benefit of enterprises.
Description
Technical Field
The invention relates to the technical field of bromine production, in particular to a process method for producing bromine by electrolyzing hydrobromic acid.
Background
Bromine is an important chemical raw material, and has wide application in the industries of flame retardants, fire extinguishing agents, refrigerants, photosensitive materials, medicines, pesticides, oil fields and the like. At present, a bromination reaction is used for preparing bromide, and hydrobromic acid which is a byproduct of the bromination reaction is commonly used for producing bromine, particularly, chlorine is used for oxidizing the hydrobromic acid and then distilling to extract bromine.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: aiming at the defects in the prior art, the process method for producing bromine by electrolyzing hydrobromic acid is provided, the use of chlorine is not needed in the whole process, a large amount of acidic wastewater is not generated, the pressure on the environment is low, and the economic benefit of enterprises is improved.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the process method for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: pumping a hydrobromic acid solution into the bottom of an electrolytic cell according to a certain flow rate, enabling generated hydrogen to enter a hydrogen washing tower from the top of the electrolytic cell, removing a small amount of bromine gas, and storing the hydrogen, dissolving the generated bromine in the hydrobromic acid solution to form a mixed solution, and enabling the mixed solution to enter a bromine evaporation tower from an overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through the packing layer and is heated by steam which passes through the bottom of the bromine steaming tower from top to bottom by virtue of gravity;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, then the mixed solution enters a bromine condenser from the top of the bromine evaporation tower, and the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
Preferably, in the step a, process water is introduced into the hydrogen washing tower to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and the obtained hydrogen washing tower absorption liquid is added into the bromine steaming tower again to be distilled.
Preferably, the bromine water in the upper layer of the bromine-water separation bottle in the step D enters the bromine distilling tower through water seal for distillation again.
Preferably, the noncondensable gas generated in the step C is treated by process water in a noncondensable gas washing tower, and the obtained noncondensable gas washing tower absorption liquid enters the bromine distilling tower again for distillation.
Preferably, U-shaped water seal structures are arranged on a connecting pipeline between the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline between the bromine-water separation bottle and the bromine steaming tower, and a connecting pipeline between the electrolytic bath and the bromine steaming tower.
Preferably, the concentration of the hydrobromic acid solution is 10-15%.
Preferably, a cathode end plate and an anode end plate which are arranged in parallel are arranged in the electrolytic cell, the cathode end plate and a wiring end plate at the upper part of the anode end plate are respectively connected with the negative electrode and the positive electrode of an external power supply, a plurality of groups of unit cells are arranged between the cathode end plate and the anode end plate, each unit cell comprises an anode plate and a cathode plate, the anode plates and the cathode plates are connected together through a connecting plate, and the cathode end plate, the unit cells and the anode end plate are arranged in a manner of alternately arranging the cathode and the anode;
the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with first fixing holes which are matched with each other, and the cathode end plate, the anode plate, the cathode plate and the anode end plate are connected together through nonmetal bolts penetrating through the first fixing holes.
Preferably, the pumping flow rate of the hydrobromic acid solution in the step A is 1 m (the number of the unit tanks +1)3/h。
Preferably, the pressure of the steam in the step B is 0.60-0.65 Mpa, and the temperature of the top of the bromine distilling tower is controlled at 85-90 ℃.
Preferably, adjacent the negative pole end plate with between the unit groove, adjacent two between the unit groove and adjacent the unit groove with all be equipped with a plurality of insulating spacers between the positive pole end plate, insulating spacer passes first fixed orifices just passes through non-metal bolt is fixed.
Preferably, an insulating partition plate is arranged between an anode plate and a cathode plate of the unit cell, the shape of the insulating partition plate is matched with the shapes of the anode plate and the cathode plate, and the insulating partition plate is provided with a plurality of second fixing holes matched with the first fixing holes;
preferably, the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with an upper row, a middle row and a lower row of first fixing holes, and the insulating partition plate is provided with an upper row, a middle row and a lower row of second fixing holes.
Preferably, the anode end plate, the cathode end plate, the anode plate, the cathode plate, the wiring end plate and the connecting plate are all titanium plates, and the surfaces of the titanium plates are all provided with precious metal coatings.
Preferably, the anode end plate, the cathode end plate, the anode plate and the cathode plate are all provided with a plurality of through holes.
Due to the adoption of the technical scheme, the invention has the beneficial effects that:
the invention relates to a process method for producing bromine by electrolyzing hydrobromic acid, which is characterized in that hydrobromic acid solution is pumped into the bottom of an electrolytic tank according to a certain flow rate, mixed solution obtained by electrolysis passes through a packing layer after being sprayed in a bromine evaporation tower and is heated by steam from bottom to top by virtue of gravity, bromine in the mixed solution is evaporated in the bromine evaporation tower and mixed with partial water vapor, then the bromine enters a bromine condenser from the top of the bromine evaporation tower, and in the bromine condenser, the bromine vapor and the water vapor are condensed into liquid to form a mixture of water and bromine, and then the mixture enters a bromine-water separation bottle for separation, so that bromine is obtained. The whole process does not need to add chlorine with larger potential safety hazard as a raw material, reduces the potential safety hazard in the storage and use processes of the chlorine, does not produce acidic wastewater, does not need subsequent treatment, fully utilizes resources, does not damage the environment, better meets the requirement of environmental protection, and improves the economic benefit of enterprises.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation. Prevent that bromine gas from causing the harm to the environment after hydrogen diffuses to the outside of electrolysis trough, bromine gas gets into again after being absorbed and evaporates the bromine tower and distill and retrieve, has avoided the waste of raw materials, and the cost has been practiced thrift to the hydrogen after the while purifies can recycle.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again. The bromine-water separation bottle has the advantages that the upper bromine-water separation bottle can prevent the volatilization of the lower bromine, the bromine-water separation bottle can continuously discharge the bromine-water to the bromine evaporation tower along with the rising of the liquid level of the bromine-water separation bottle, and the bromine in the bromine-water separation bottle is recovered through secondary distillation.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation. The noncondensable gas washing tower can wash part of bromine gas to form noncondensable gas washing tower absorption liquid, then the noncondensable gas washing tower absorption liquid is discharged into the bromine steaming tower to be distilled again, bromine is recycled again, and resource waste is avoided.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower. The U-shaped water seal structure can reduce volatilization of bromine and bromine steam when the bromine and the bromine steam flow in the pipeline, thereby avoiding product waste and simultaneously reducing the potential safety hazard of bromine explosion.
The concentration of the hydrobromic acid solution is 10-15%. The electrode of the electrolytic cell and the noble metal coating thereof are damaged due to overhigh concentration of the hydrobromic acid, and the conductivity of the hydrobromic acid solution is weakened due to overlow concentration of the hydrobromic acid, so that the voltage of the electrolytic cell is increased, and the power consumption of production is increased.
The electrolytic cell is characterized in that a cathode end plate and an anode end plate which are arranged in parallel are arranged in the electrolytic cell, the cathode end plate and a wiring end plate on the upper part of the anode end plate are respectively connected with a negative electrode and a positive electrode of an external power supply, a plurality of groups of unit cells are arranged between the cathode end plate and the anode end plate, each unit cell comprises an anode plate and a cathode plate, the anode plates and the cathode plates are connected together through a connecting plate, and the cathode end plate, the unit cells and the anode end plate are arranged in a positive-negative alternative arrangement mode; the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with first fixing holes which are matched with each other, and the cathode end plate, the anode plate, the cathode plate and the anode end plate are connected together through nonmetal bolts penetrating through the first fixing holes. After the external power supply applies voltage to the cathode end plate and the anode end plate, current is conducted among the unit tanks through electrolyte, the anode plates and the cathode plates of the unit tanks are connected through the connecting plate, namely, contact voltage drop does not exist between the two electrode plates, electric energy is saved, low-voltage low-current operation is realized, potential safety hazards are small, the unit tanks are assembled in an integrated mode, manufacturing cost of the electrolytic tanks is saved, and production cost is reduced.
The pumping flow rate of the hydrobromic acid solution in the step A is 1 (the number of the unit tanks +1) m3H is used as the reference value. Ensuring the speed of the hydrobromic acid solution pumped into the electrolytic tankThe electrolytic speed of the electrolytic tank is matched, and the composition proportion of the mixed liquid in the electrolytic tank is ensured to be in a stable range.
And B, controlling the pressure of the steam to be 0.60-0.65 Mpa, controlling the temperature of the top of the bromine steaming tower to be 85-90 ℃, and adjusting the flow of the steam according to the content of molecular bromine in the residual liquid at the bottom of the bromine steaming tower and the temperature of the top of the bromine steaming tower so as to ensure that the discharge temperature of the top of the bromine steaming tower is in a stable state.
Adjacent the negative pole end plate with between the unit cell, adjacent two between the unit cell and adjacent the unit cell with all be equipped with a plurality of insulating spacers between the positive pole end plate, insulating spacer passes first fixed orifices just passes through non-metallic bolt is fixed. The distances between the adjacent cathode end plates and the unit cells, between the adjacent two unit cells and between the adjacent unit cells and the anode end plates can be adjusted by adjusting the thickness of the insulating spacers, so that the optimal electrolysis efficiency is ensured.
An insulating partition plate is arranged between the anode plate and the cathode plate of the unit tank, the shape of the insulating partition plate is matched with the shapes of the anode plate and the cathode plate, and the insulating partition plate is provided with a plurality of second fixing holes matched with the first fixing holes; the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with an upper row, a middle row and a lower row of first fixing holes, and the insulating partition plate is provided with an upper row, a middle row and a lower row of second fixing holes. The insulating partition board is arranged between the adjacent electrolysis units, so that the possibility that the anode product is dissociated to the cathode and reduced is avoided, the electrolysis efficiency is greatly improved, the whole electrolysis period is shortened, and the production efficiency is improved. Through the first fixed orifices of three rows and the second fixed orifices that set up about last, the fixed more firm between end plate and unit cell and the insulating barrier has improved the durability in use of equipment.
The anode end plate, the cathode end plate, the anode plate, the cathode plate, the terminal plate and the connecting plate are titanium plates, and the surfaces of the titanium plates and the connecting plate are provided with precious metal coatings. The titanium material has stable performance and strong corrosion resistance, is particularly suitable for being used in acidic or alkaline electrolyte, and has good conductivity of the noble metal coating, high activity of the coating, good uniformity and long service life.
The anode end plate, the cathode end plate, the anode plate and the cathode plate are all provided with a plurality of through holes. The gas that the electrolysis produced can see through the through-hole and will adhere to the electrolysis product on end plate and electrode board and rush down at the rising in-process, prevents that the electrolysis product from piling up on end plate and electrode board, causes the electric conductivity of end plate and electrode board to become low, influences the efficiency of electrolysis.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a process flow diagram of an embodiment of the invention;
FIG. 2 is a schematic view of the construction of an electrolytic apparatus in example 1 of the present invention;
FIG. 3 is a schematic structural view of the anode end plate of FIG. 2;
FIG. 4 is a front view of the cell slot of FIG. 2;
FIG. 5 is a left side view of the cell slot of FIG. 2;
FIG. 6 is a schematic view of the structure of the insulating spacer of FIG. 2;
wherein: 1. a cathode end plate; 2. an anode end plate; 3. a terminal plate; 4. a unit cell; 5. an anode plate; 6. a cathode plate; 7. a connecting plate; 8. a first fixing hole; 9. a non-metallic bolt; 10. an insulating spacer; 11. an insulating spacer; 12. a second fixing hole; 13. and a through hole.
Detailed Description
The invention is further illustrated by the following examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
As shown in fig. 2 to 6, an electrolytic cell comprises a closed outer shell, an electrolytic device is arranged inside the outer shell, an electrolyte inlet is arranged at the bottom of the electrolytic cell, a liquid overflow port is arranged at the upper part of the electrolytic cell, and a gas outlet is arranged at the top of the electrolytic cell.
The electrolysis device comprises a cathode end plate 1 and an anode end plate 2 which are arranged in parallel, wherein a wiring end plate 3 on the upper parts of the cathode end plate 1 and the anode end plate 2 are respectively connected with a negative electrode and a positive electrode of an external power supply, in the embodiment, four groups of unit grooves 4 are arranged between the cathode end plate 1 and the anode end plate 2, each unit groove 4 comprises an anode plate 5, a cathode plate 6 and a U-shaped connecting plate 7 respectively connected with the anode plate 5 and the cathode plate 6, the anode plate 5 and the cathode plate 6 are respectively welded with two open ends of the connecting plate 7, and the cathode end plate 1, the unit grooves 4 and the anode end plate 2 are arranged in a mode of alternately arranging in a positive-negative mode; the anode end plate 2, the cathode end plate 1, the anode plate 5 and the cathode plate 6 are all provided with first fixing holes 8 which are matched with each other, and the cathode end plate 1, the anode plate 5, the cathode plate 6 and the anode end plate 2 are connected together through non-metal bolts 9 penetrating through the first fixing holes 8.
In the embodiment, the distance between the anode plate 5 and the cathode plate 6 in the unit tank 4 is 10mm, the lengths of the anode plate 5, the cathode plate 6, the anode end plate 2 and the cathode end plate 1 are 240mm, the height is 380mm, the thickness is 2mm, and the sizes of the parts can be scaled according to actual production scale.
Adjacent the negative pole end plate 1 with between the unit groove 4, adjacent two between the unit groove 4 and adjacent unit groove 4 with all be equipped with a plurality of insulating spacers 10 between the positive pole end plate 2, insulating spacers 10 pass first fixed orifices 8 just pass through nonmetal bolt 9 is fixed.
An insulating partition plate 11 is arranged between the anode plate 5 and the cathode plate 6 of the unit tank 4, the shape of the insulating partition plate 11 is matched with the shapes of the anode plate 5 and the cathode plate 6, and the insulating partition plate 11 is provided with a plurality of second fixing holes 12 matched with the first fixing holes 8; the anode end plate 2, the cathode end plate 1, the anode plate 5 and the cathode plate 6 are provided with an upper row, a middle row and a lower row of first fixing holes 8, and the insulating partition plate 11 is provided with an upper row, a middle row and a lower row of second fixing holes 12.
The anode end plate 2, the cathode end plate 1, the anode plate 5, the cathode plate 6, the terminal plate 3 and the connecting plate 7 are titanium plates, and the surfaces of the titanium plates are provided with precious metal coatings.
The anode end plate 2, the cathode end plate 1, the anode plate 5 and the cathode plate 6 are all provided with a plurality of through holes 13.
Example 2
As shown in fig. 1, the process for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: the hydrobromic acid solution with the concentration of 10% is processed according to the proportion of 5m3The flow rate of the hydrogen per hour is pumped into the bottom of the electrolytic cell in the embodiment 1, the generated hydrogen enters a hydrogen washing tower from a gas outlet at the top of the electrolytic cell and is stored after a small amount of bromine is removed, and the generated bromine is dissolved in hydrobromic acid solution to form a mixed solution and enters a bromine steaming tower from a liquid overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through a filler layer and is heated by steam which passes through the bottom of the bromine steaming tower from bottom to top by virtue of gravity, and the pressure of the steam is 0.60 Mpa;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, and then enters a bromine condenser from the top of the bromine evaporation tower, the temperature of the top of the bromine evaporation tower is controlled at 85 ℃, the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank, the dilute hydrobromic acid can be used for absorbing hydrobromic acid gas generated by bromination reaction, so that the concentration of the hydrobromic acid gas meets the requirement, the electrolysis reaction is repeatedly carried out, and no waste is generated in the whole process;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower.
Example 3
As shown in fig. 1, the process for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: the hydrobromic acid solution with the concentration of 12% is processed according to the proportion of 5m3The flow rate of the hydrogen per hour is pumped into the bottom of the electrolytic cell in the embodiment 1, the generated hydrogen enters a hydrogen washing tower from a gas outlet at the top of the electrolytic cell and is stored after a small amount of bromine is removed, and the generated bromine is dissolved in hydrobromic acid solution to form a mixed solution and enters a bromine steaming tower from a liquid overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through a filler layer and is heated by steam which passes through the bottom of the bromine steaming tower from bottom to top by virtue of gravity, and the pressure of the steam is 0.60 Mpa;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, and then enters a bromine condenser from the top of the bromine evaporation tower, the temperature of the top of the bromine evaporation tower is controlled at 85 ℃, the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank, the dilute hydrobromic acid can be used for absorbing hydrobromic acid gas generated by bromination reaction, so that the concentration of the hydrobromic acid gas meets the requirement, the electrolysis reaction is repeatedly carried out, and no waste is generated in the whole process;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower.
Example 4
As shown in fig. 1, the process for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: adding 15% hydrobromic acid solution according to 5m3The flow rate of the hydrogen per hour is pumped into the bottom of the electrolytic cell in the embodiment 1, the generated hydrogen enters a hydrogen washing tower from a gas outlet at the top of the electrolytic cell and is stored after a small amount of bromine is removed, and the generated bromine is dissolved in hydrobromic acid solution to form a mixed solution and enters a bromine steaming tower from a liquid overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through a filler layer and is heated by steam which passes through the bottom of the bromine steaming tower from bottom to top by virtue of gravity, and the pressure of the steam is 0.60 Mpa;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, and then enters a bromine condenser from the top of the bromine evaporation tower, the temperature of the top of the bromine evaporation tower is controlled at 85 ℃, the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank, the dilute hydrobromic acid can be used for absorbing hydrobromic acid gas generated by bromination reaction, so that the concentration of the hydrobromic acid gas meets the requirement, the electrolysis reaction is repeatedly carried out, and no waste is generated in the whole process;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower.
Example 5
As shown in fig. 1, the process for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: adding 15% hydrobromic acid solution according to 5m3The flow rate of the hydrogen per hour is pumped into the bottom of the electrolytic cell in the embodiment 1, the generated hydrogen enters a hydrogen washing tower from a gas outlet at the top of the electrolytic cell and is stored after a small amount of bromine is removed, and the generated bromine is dissolved in hydrobromic acid solution to form a mixed solution and enters a bromine steaming tower from a liquid overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through a filler layer and is heated by steam which passes through the bottom of the bromine steaming tower from bottom to top by virtue of gravity, and the pressure of the steam is 0.65 Mpa;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, and then enters a bromine condenser from the top of the bromine evaporation tower, the temperature of the top of the bromine evaporation tower is controlled at 85 ℃, the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank, the dilute hydrobromic acid can be used for absorbing hydrobromic acid gas generated by bromination reaction, so that the concentration of the hydrobromic acid gas meets the requirement, the electrolysis reaction is repeatedly carried out, and no waste is generated in the whole process;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower.
Example 6
As shown in fig. 1, the process for producing bromine by electrolyzing hydrobromic acid comprises the following steps:
a: adding 15% hydrobromic acid solution according to 5m3The flow rate of the hydrogen per hour is pumped into the bottom of the electrolytic cell in the embodiment 1, the generated hydrogen enters a hydrogen washing tower from a gas outlet at the top of the electrolytic cell and is stored after a small amount of bromine is removed, and the generated bromine is dissolved in hydrobromic acid solution to form a mixed solution and enters a bromine steaming tower from a liquid overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through a filler layer and is heated by steam which passes through the bottom of the bromine steaming tower from bottom to top by virtue of gravity, and the pressure of the steam is 0.65 Mpa;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, and then enters a bromine condenser from the top of the bromine evaporation tower, the temperature of the top of the bromine evaporation tower is controlled at 90 ℃, the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank, the dilute hydrobromic acid can be used for absorbing hydrobromic acid gas generated by bromination reaction, so that the concentration of the hydrobromic acid gas meets the requirement, the electrolysis reaction is repeatedly carried out, and no waste is generated in the whole process;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
And B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
And D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
And D, allowing the noncondensable gas generated in the step C to pass through process water in a noncondensable gas washing tower to obtain noncondensable gas washing tower absorption liquid, and allowing the noncondensable gas washing tower absorption liquid to enter a bromine distilling tower again for distillation.
U-shaped water seal structures are arranged on a connecting pipeline of the bromine steaming tower and the dilute hydrobromic acid storage tank, a connecting pipeline of the bromine-water separation bottle and the bromine steaming tower and a connecting pipeline of the electrolytic bath and the bromine steaming tower.
The process control parameters of examples 2-6 were used, and the process index was taken over 1 hour after the system was stabilized, to obtain the following results:
TABLE 1
As can be seen from table 1, when the electrolytic cell of example 1 is used, the yield of bromine is more than 98%, the power consumption during electrolysis is low, the cost is saved, the contact voltage drop between the anode plate and the cathode plate does not exist, the operating voltage of the electrolytic cell is reduced, the concentration of dilute hydrobromic acid is low, and the hydrobromic acid solution is fully electrolyzed in the electrolytic cell, and the electrolytic efficiency is high. Compared with the conventional chlorine oxidation process for preparing the bromine, the method disclosed by the invention has the advantages that the trouble of treating the acidic wastewater is saved, and the pressure on the environment is greatly reduced.
Claims (10)
1. The process method for producing bromine by electrolyzing hydrobromic acid is characterized by comprising the following steps:
a: pumping a hydrobromic acid solution into the bottom of an electrolytic cell according to a certain flow rate, enabling generated hydrogen to enter a hydrogen washing tower from the top of the electrolytic cell, removing a small amount of bromine gas, and storing the hydrogen, dissolving the generated bromine in the hydrobromic acid solution to form a mixed solution, and enabling the mixed solution to enter a bromine evaporation tower from an overflow port at the top of the electrolytic cell;
b: the mixed solution is sprayed in the bromine steaming tower, passes through the packing layer and is heated by steam which passes through the bottom of the bromine steaming tower from top to bottom by virtue of gravity;
c: bromine in the mixed solution is evaporated in a bromine evaporation tower and mixed with part of water vapor, then the mixed solution enters a bromine condenser from the top of the bromine evaporation tower, and the mixed solution after bromine evaporation reaches the bottom of the bromine evaporation tower to become dilute hydrobromic acid and is discharged to a dilute hydrobromic acid storage tank;
d: in the bromine condenser, bromine steam and water vapor are condensed into liquid to form a mixture of water and bromine, and the mixture enters a bromine-water separation bottle for separation to obtain bromine.
2. The process for the electrolytic production of bromine from hydrobromic acid as claimed in claim 1 wherein: and B, introducing process water into the hydrogen washing tower in the step A to absorb a small amount of bromine gas to obtain hydrogen washing tower absorption liquid, and adding the obtained hydrogen washing tower absorption liquid into the bromine steaming tower again for distillation.
3. The process for the electrolytic production of bromine from hydrobromic acid as claimed in claim 1 wherein: and D, allowing the bromine water on the upper layer in the bromine-water separation bottle in the step D to enter a bromine evaporation tower through water seal for distillation again.
4. The process for the electrolytic production of bromine from hydrobromic acid as claimed in claim 1 wherein: the concentration of the hydrobromic acid solution is 10-15%.
5. The process for the electrolytic production of bromine from hydrobromic acid as claimed in claim 1 wherein: the electrolytic cell is characterized in that a cathode end plate and an anode end plate which are arranged in parallel are arranged in the electrolytic cell, the cathode end plate and a wiring end plate on the upper part of the anode end plate are respectively connected with a negative electrode and a positive electrode of an external power supply, a plurality of groups of unit cells are arranged between the cathode end plate and the anode end plate, each unit cell comprises an anode plate and a cathode plate, the anode plates and the cathode plates are connected together through a connecting plate, and the cathode end plate, the unit cells and the anode end plate are arranged in a positive-negative alternative arrangement mode;
the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with first fixing holes which are matched with each other, and the cathode end plate, the anode plate, the cathode plate and the anode end plate are connected together through nonmetal bolts penetrating through the first fixing holes.
6. The process for the electrolytic production of bromine from hydrobromic acid as in claim 5 wherein: the pumping flow rate of the hydrobromic acid solution in the step A is 1 (the number of the unit tanks +1) m3/h。
7. The process for the electrolytic production of bromine from hydrobromic acid as in claim 5 wherein: adjacent the negative pole end plate with between the unit cell, adjacent two between the unit cell and adjacent the unit cell with all be equipped with a plurality of insulating spacers between the positive pole end plate, insulating spacer passes first fixed orifices just passes through non-metallic bolt is fixed.
8. The process for the electrolytic production of bromine from hydrobromic acid as in claim 5 wherein: an insulating partition plate is arranged between the anode plate and the cathode plate of the unit tank, the shape of the insulating partition plate is matched with the shapes of the anode plate and the cathode plate, and the insulating partition plate is provided with a plurality of second fixing holes matched with the first fixing holes;
the anode end plate, the cathode end plate, the anode plate and the cathode plate are provided with an upper row, a middle row and a lower row of first fixing holes, and the insulating partition plate is provided with an upper row, a middle row and a lower row of second fixing holes.
9. The process for the electrolytic production of bromine from hydrobromic acid as in claim 5 wherein: the anode end plate, the cathode end plate, the anode plate, the cathode plate, the terminal plate and the connecting plate are titanium plates, and the surfaces of the titanium plates and the connecting plate are provided with precious metal coatings.
10. The process for the electrolytic production of bromine from hydrobromic acid as in claim 5 wherein: the anode end plate, the cathode end plate, the anode plate and the cathode plate are all provided with a plurality of through holes.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117552020A (en) * | 2023-12-29 | 2024-02-13 | 潍坊东元连海环保科技有限公司 | Bromine preparation method of sodium bromide |
| CN117680068A (en) * | 2024-02-01 | 2024-03-12 | 山东润宏新材料有限公司 | Bromination treatment reaction kettle |
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| CN1771353A (en) * | 2003-03-31 | 2006-05-10 | 科学和工业研究委员会 | A process for electrochemical oxidation of bromide to bromine |
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| US5039383A (en) * | 1989-04-20 | 1991-08-13 | W. R. Grace & Co.-Conn. | Halogen generation |
| US5833834A (en) * | 1996-04-08 | 1998-11-10 | Solar Reactor Technologies | Method for generating hydrogen from HBR |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN117552020A (en) * | 2023-12-29 | 2024-02-13 | 潍坊东元连海环保科技有限公司 | Bromine preparation method of sodium bromide |
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| CN117680068B (en) * | 2024-02-01 | 2024-04-19 | 山东润宏新材料有限公司 | Bromination treatment reaction kettle |
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