CN111285331A - Method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process - Google Patents
Method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process Download PDFInfo
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- CN111285331A CN111285331A CN201811496103.6A CN201811496103A CN111285331A CN 111285331 A CN111285331 A CN 111285331A CN 201811496103 A CN201811496103 A CN 201811496103A CN 111285331 A CN111285331 A CN 111285331A
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- bromine
- hydrobromic acid
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- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 title claims abstract description 122
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 97
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 74
- 239000012267 brine Substances 0.000 title claims abstract description 50
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 50
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004821 distillation Methods 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims description 30
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 21
- 239000000126 substance Substances 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- 229910052801 chlorine Inorganic materials 0.000 claims description 12
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 238000007664 blowing Methods 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 6
- 235000019254 sodium formate Nutrition 0.000 claims description 6
- 239000004280 Sodium formate Substances 0.000 claims description 5
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 4
- 229940039790 sodium oxalate Drugs 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 239000001632 sodium acetate Substances 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 2
- -1 salt lakes Chemical compound 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 7
- 239000013535 sea water Substances 0.000 abstract description 4
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 18
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 11
- 239000003513 alkali Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical group OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011265 semifinished product Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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Classifications
-
- 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
- C01B7/093—Hydrogen bromide
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/10—Bromides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of resource utilization of bromine-containing brine such as salt lakes, seawater, underground brine, industrial wastewater and the like, and particularly provides a short-process preparation method of hydrobromic acid and sodium bromide from the bromine-containing brine. The process mainly comprises the following steps: oxidizing bromine-containing brine, absorbing by alkaline solution, preparing hydrobromic acid by distillation, preparing sodium bromide by crystallization and the like. The technology provides a brand-new technical scheme for preparing the hydrobromic acid and the sodium bromide by extracting bromine from the brine, greatly shortens the process flow compared with the traditional process, and has the advantages of simple process, easy industrialization and wide application prospect.
Description
Technical Field
The invention belongs to the field of resource utilization of bromine-containing brine such as salt lakes, seawater, underground brine, industrial wastewater and the like, and relates to a technology for preparing hydrobromic acid and sodium bromide from the bromine-containing brine in a short process. The technology provides a brand-new process scheme for preparing hydrobromic acid and sodium bromide by extracting bromine from brine, and mainly comprises links of oxidizing bromine-containing brine, absorbing alkaline solution, preparing the hydrobromic acid by distillation, preparing the sodium bromide by crystallization and the like.
Background
Bromine is used as an important chemical raw material and has wide application in the fields of fine chemical industry, medicine, agriculture, military industry and the like, and the bromine production raw material mainly comes from seawater, underground brine and salt lake brine. Currently, the main methods for producing bromine include: air blowing method, steam distillation method, air blowing method, resin adsorption method, liquid membrane method, gaseous membrane method, air blowing membrane method, ion exchange method, and the like. Bromine extraction from brine generally requires a plurality of unit operation steps such as oxidation, rectification, condensation, washing and the like, and the whole process is complex and has high energy consumption.
Hydrobromic acid and sodium bromide are two important bromine downstream products and have very wide application.
The hydrobromic acid can be produced by adopting bromine and different reducing agent raw materials, the production method is more, the same point of various methods is that a hydrobromic acid semi-finished product is prepared firstly, and then the hydrobromic acid finished product is obtained by refining, the currently common industrial production methods mainly comprise ① red phosphorus method, namely a red phosphorus reacts with bromine in water, ② primary acid method, namely a bromide (sodium or potassium salt) reacts with sulfuric acid at a constant boiling point, ③ sulfur dioxide method, namely a sulfur dioxide and bromine react at a low temperature, ④ synthesis method, namely a hydrogen and bromine directly react, ⑤ secondary hydrobromic acid, namely hydrogen bromide gas is a byproduct in some organic synthesis reaction processes with bromine participation, and the byproduct after water absorption is the secondary hydrogen bromic acid.
The preparation method of sodium bromide can be divided into several methods such as neutralization method, reduction method and ion exchange method. The neutralization method can be divided into two methods according to different raw materials: one process is to react sodium hydroxide with hydrobromic acid; the second is the reaction of sodium carbonate with hydrobromic acid. The reducing agent adopted by the reduction method mainly comprises urea, hydrogen peroxide, scrap iron and sodium oxalate, and currently, urea is mostly adopted as the reducing agent in the industry. The prior preparation process of sodium bromide mainly comprises a neutralization method and a urea reduction method.
The research provides a new technological process for synthesizing HBr and NaBr, and adopts the direct reaction of alkaline substances and bromine to prepare two products in one step, thereby greatly shortening the technological process.
Disclosure of Invention
The invention provides a short-process method for preparing hydrobromic acid and sodium bromide from bromine-containing brine, and realizes short-process resource utilization of the bromine-containing brine.
The above purpose is realized by the following technical scheme:
a technology for preparing hydrobromic acid and sodium bromide from bromine-containing brine in a short process is characterized in that: oxidizing bromine-containing brine by chlorine or other strong oxidants, oxidizing bromine ions into bromine simple substance, blowing out air, reacting the bromine simple substance with alkaline solution, reacting and absorbing to form NaBr-HBr-H2And (3) an O solution system, wherein HBr is separated out by the system through distillation and top flow to obtain a hydrobromic acid product, meanwhile, NaBr is concentrated, and the concentrated NaBr solution is evaporated and crystallized to prepare a NaBr product.
The raw materials in the technical scheme are bromine-containing brine such as salt lake, seawater, underground brine, industrial wastewater and the like. Oxidizing bromine-containing brine under acidic condition, and controlling pH value to be 0-6.5. The adopted oxidant is chlorine, sodium hypochlorite, hydrogen peroxide or other strong oxidant, preferably chlorine.
The oxidation reaction principle is as follows:
NaBr+Cl2→Br2+NaCl
the bromine exists in the brine, and air blowing can be adopted by utilizing the characteristic that the bromine is easy to volatilize. And (3) allowing the air carrying the gaseous free bromine to enter an absorption tower and adopting an alkaline solution for reaction and absorption. Taking sodium formate as an example, the reaction principle is as follows:
HCOONa+Br2→NaBr+HBr+CO2
after the alkaline substance reacts with the bromine simple substance and is absorbed, NaBr-HBr-H is formed2O is a solution system with the main component. The NaBr-HBr-H2And (3) distilling the O solution system under normal pressure or reduced pressure, and separating HBr from the top flow by adopting an intermittent or continuous rectification mode to obtain a hydrobromic acid product. NaBr-HBr-H2In the O solution system, NaBr is concentrated in the distillation process, and the concentrated NaBr solution is evaporated and crystallized to prepare a NaBr product.
According to the short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine, air is blown out from an oxidized brine raw material solution, air carrying gaseous free bromine enters an absorption tower, and alkaline substances which are reacted and absorbed with a bromine simple substance are one or more of sodium hydroxide, sodium carbonate, ammonium bicarbonate, sodium formate, sodium acetate, sodium oxalate and sodium sulfide.
The beneficial technical effects are as follows:
1. simplifying the preparation steps and reducing the production energy consumption. The traditional technology for preparing hydrobromic acid and sodium bromide is to prepare bromine from brine through a complex process and then prepare the hydrobromic acid and the sodium bromide from the bromine through the complex process. The invention provides a novel process flow for synthesizing hydrobromic acid and sodium bromide, which adopts the direct reaction of alkaline substances and bromine blown out by air to prepare two products in one step, reduces the conventional lengthy multi-step reaction separation steps into one-step oxidation, reduces the use amount of oxidants such as chlorine and the like, and reduces the energy consumption and the generation of polluting waste gas.
2. The products NaBr and HBr are easy to separate and are important chemical raw materials.
3. The influence of sulfate ions is excluded. The raw materials do not contain sulfate radicals, so the obtained hydrobromic acid product has low sulfur impurity content.
Drawings
FIG. 1 is a simplified process diagram of a short process for preparing hydrobromic acid and sodium bromide from bromine-containing brine.
Detailed Description
The invention provides a technology for preparing hydrobromic acid and sodium bromide from bromine-containing brine in a short process. The technology provides a brand-new process scheme for preparing HBr and NaBr by extracting bromine from brine.
As shown in fig. 1, in the embodiment, the process mainly includes steps of oxidizing bromine-containing brine, absorbing alkaline solution, preparing hydrobromic acid by distillation, preparing sodium bromide by crystallization, and the like.
Example 1: method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process
100L of raw material brine containing 950mg/L of bromine is taken and placed in a 150L oxidation reactor, sulfuric acid, hydrochloric acid or nitric acid is added under the condition of normal temperature, the pH value is adjusted to be controlled between 0 and 6.5, chlorine is blown in under the acidic condition, the flow rate of the blown chlorine is 5L/min, and bromine ions are oxidized into bromine simple substances.
The oxidized bromine-containing raw material liquid enters a blow-out tower from the top of the blow-out tower (the diameter is 60mm, the height is 1500mm) through a spraying device, meanwhile, air enters the blow-out tower from the bottom of the blow-out tower through an air blower, the gas-liquid ratio of the blown air to the sprayed raw material liquid is 100, and the air-liquid ratio is in countercurrent contact with the bromine-containing raw material liquid, so that gaseous free bromine is analyzed. The air carrying gaseous free bromine enters an absorption tower (diameter is 60mm, height is 1500mm), and is in countercurrent contact with absorption alkali liquor or in parallel flow contact with the absorption alkali liquor and absorbed, and the reaction and absorption form NaBr-HBr-H2And (4) O solution system. The alkaline substance which reacts with the bromine and is absorbed is one or more of sodium hydroxide, sodium carbonate, ammonium bicarbonate, sodium formate, sodium acetate, sodium oxalate and sodium sulfide. The extraction rate of bromine in the process reaches 85% -95%.
And (3) the absorption liquid enters a distillation tower (the diameter is 30mm, the height is 1500mm), and the absorption liquid is subjected to atmospheric or vacuum distillation, and a top flow is obtained by distillation in a batch or continuous rectification mode, and HBr is separated to obtain a hydrobromic acid product.
Concentrating NaBr during the distillation process, placing the concentrated NaBr solution in a 10L crystallizer for evaporation crystallization, and cooling, filtering and drying to obtain a NaBr product.
Example 2: method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process
100L of raw material brine containing 950mg/L of bromine is put into a 150L oxidation reactor, sulfuric acid is added under the condition of normal temperature, the pH value is adjusted to be 0-6.5, chlorine is blown in under the acidic condition, the flow rate of the blown chlorine is 10L/min, and bromine ions are oxidized into bromine simple substance.
The oxidized bromine-containing raw material liquid enters a blow-off tower from the top of the blow-off tower (the diameter is 60mm, the height is 1500mm) through a spraying device, and meanwhile, air enters the blow-off tower from the bottom of the tower through an air blower and is in countercurrent contact with the bromine-containing raw material liquid, so that gaseous free bromine is analyzed out. The air carrying gaseous free bromine enters an absorption tower (diameter is 60mm, height is 1500mm), and is in countercurrent contact with absorption alkali liquor or in parallel flow contact with the absorption alkali liquor and absorbed, and the reaction and absorption form NaBr-HBr-H2And (4) O solution system. The alkaline substance which reacts with the bromine and is absorbed is sodium carbonate. The extraction rate of bromine in the process reaches 85% -95%.
And (3) the absorption liquid enters a distillation tower (the diameter is 30mm, the height is 1500mm), and the absorption liquid is subjected to atmospheric or vacuum distillation, and a top flow is obtained by distillation in a batch or continuous rectification mode, and HBr is separated to obtain a hydrobromic acid product.
Concentrating NaBr during the distillation process, placing the concentrated NaBr solution in a 10L crystallizer for evaporation crystallization, and cooling, filtering and drying to obtain a NaBr product.
Example 3: method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process
100L of raw material brine containing 950mg/L of bromine is taken and placed in a 150L oxidation reactor, hydrochloric acid is added under the condition of 30 ℃, the pH value is adjusted to be 3, chlorine is blown in under the acidic condition, the flow rate of the blown chlorine is 10L/min, and bromine ions are oxidized into bromine simple substances.
The oxidized bromine-containing raw material liquid enters a blow-off tower from the top of the blow-off tower (the diameter is 60mm, the height is 1500mm) through a spraying device, and meanwhile, air enters the blow-off tower from the bottom of the tower through an air blower and is in countercurrent contact with the bromine-containing raw material liquid, so that gaseous free bromine is analyzed out. The air carrying gaseous free bromine enters an absorption tower (diameter is 60mm, height is 1500mm), and is in countercurrent contact with absorption alkali liquor or in parallel flow contact with the absorption alkali liquor and absorbed, and the reaction and absorption form NaBr-HBr-H2O solutionAnd (4) a liquid system. The alkaline substance which reacts with the bromine simple substance and is absorbed is sodium formate. The extraction rate of bromine in the process reaches 85% -95%.
And (3) the absorption liquid enters a distillation tower (the diameter is 30mm, the height is 1500mm), and the absorption liquid is subjected to atmospheric or vacuum distillation, and a top flow is obtained by distillation in a batch or continuous rectification mode, and HBr is separated to obtain a hydrobromic acid product.
Concentrating NaBr during the distillation process, placing the concentrated NaBr solution in a 10L crystallizer for evaporation crystallization, and cooling, filtering and drying to obtain a NaBr product.
Example 4: method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in short process
100L of raw material brine containing 950mg/L of bromine is taken and placed in a 150L oxidation reactor, nitric acid is added under the condition of 30 ℃, the pH value is adjusted to be 4, sodium hypochlorite is added under the acidic condition, and bromine ions are oxidized into elemental bromine.
The oxidized bromine-containing raw material liquid enters a blow-off tower from the top of the blow-off tower (the diameter is 60mm, the height is 1500mm) through a spraying device, and meanwhile, air enters the blow-off tower from the bottom of the tower through an air blower and is in countercurrent contact with the bromine-containing raw material liquid, so that gaseous free bromine is analyzed out. The air carrying gaseous free bromine enters an absorption tower (diameter is 60mm, height is 1500mm), and is in countercurrent contact with absorption alkali liquor or in parallel flow contact with the absorption alkali liquor and absorbed, and the reaction and absorption form NaBr-HBr-H2And (4) O solution system. The alkaline substances which are reacted and absorbed with the bromine are sodium hydroxide and sodium carbonate, and the adding ratio is 1: 1. The extraction rate of bromine in the process reaches 85% -95%.
And (3) the absorption liquid enters a distillation tower (the diameter is 30mm, the height is 1500mm), and the absorption liquid is subjected to atmospheric or vacuum distillation, and a top flow is obtained by distillation in a batch or continuous rectification mode, and HBr is separated to obtain a hydrobromic acid product.
Concentrating NaBr during the distillation process, placing the concentrated NaBr solution in a 10L crystallizer for evaporation crystallization, and cooling, filtering and drying to obtain a NaBr product.
The above examples, which are used in conjunction with the drawings to describe the process flow of the present invention in detail, are only used for illustrating and helping to understand the feasibility of the process of the present invention, and do not limit the protection scope of the present invention, and can be adjusted and modified accordingly according to different target requirements, and all designs identical or similar to the present invention are within the protection scope of the present invention.
Claims (8)
1. A method for preparing hydrobromic acid and sodium bromide from bromine-containing brine in a short process is characterized by comprising the following steps: after the bromine-containing brine is oxidized by chlorine or other strong oxidants, bromide ions are oxidized into elemental bromine, the elemental bromine is blown out by air and reacts with alkaline solution to form NaBr-HBr-H through reaction and absorption2And (3) an O solution system, wherein HBr is separated out by the system through distillation and top flow to obtain a hydrobromic acid product, meanwhile, NaBr is concentrated, and the concentrated NaBr solution is evaporated and crystallized to prepare a NaBr product.
2. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: oxidizing bromine-containing brine under acidic condition, and controlling pH value at 0-6.5.
3. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: the bromine-containing brine is oxidized by chlorine, sodium hypochlorite, hydrogen peroxide or other strong oxidants.
4. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: and (3) oxidizing by using chlorine gas.
5. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: blowing out the oxidized brine raw material liquid by adopting air, feeding the air carrying gaseous free bromine into an absorption tower, and reacting and absorbing the air with the bromine simple substance to obtain one or more alkaline substances selected from sodium hydroxide, sodium carbonate, ammonium bicarbonate, sodium formate, sodium acetate, sodium oxalate and sodium sulfide.
6. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: after the alkaline substance reacts with the bromine simple substance and is absorbed, NaBr-HBr-H is formed2O is a solution system with the main component.
7. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: NaBr-HBr-H2And (3) distilling the O solution system under normal pressure or reduced pressure, and separating HBr from the top flow by adopting an intermittent or continuous rectification mode to obtain a hydrobromic acid product.
8. The short-process preparation method of hydrobromic acid and sodium bromide from bromine-containing brine according to claim 1, which is characterized in that: NaBr-HBr-H2In the O solution system, NaBr is concentrated in the distillation process, and the concentrated NaBr solution is evaporated and crystallized to prepare a NaBr product.
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| CN114436293A (en) * | 2022-04-12 | 2022-05-06 | 天津长芦汉沽盐场有限责任公司 | Method for directly producing sodium bromide from low-concentration brine |
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