CN111573955A - Comprehensive utilization method of concentrated seawater - Google Patents
Comprehensive utilization method of concentrated seawater Download PDFInfo
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- CN111573955A CN111573955A CN202010428956.7A CN202010428956A CN111573955A CN 111573955 A CN111573955 A CN 111573955A CN 202010428956 A CN202010428956 A CN 202010428956A CN 111573955 A CN111573955 A CN 111573955A
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- China
- Prior art keywords
- seawater
- bromine
- acidification
- chlorination
- hydrogen
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- 239000013535 sea water Substances 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 19
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 34
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 34
- 230000020477 pH reduction Effects 0.000 claims abstract description 24
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 20
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 15
- 238000004821 distillation Methods 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 239000012267 brine Substances 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 11
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 11
- 238000007664 blowing Methods 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000000909 electrodialysis Methods 0.000 claims abstract description 6
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 10
- 239000002699 waste material Substances 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 238000002360 preparation method Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 235000002639 sodium chloride Nutrition 0.000 description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000011780 sodium chloride Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000012528 membrane 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
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a method for comprehensively utilizing concentrated seawater, which is characterized in that concentrated seawater is used as a raw material for bromine extraction production, acidic seawater in the bromine extraction process is neutralized by alkali liquor and then is subjected to ultrafiltration, electrodialysis concentration and other processes to obtain concentrated brine, the concentrated brine can be used for preparing refined salt and food-grade low-sodium salt by a salt preparation process, the refined salt can be electrolyzed to generate liquid alkali, hydrogen and chlorine, the alkali liquor can be used for blowing bromine absorption liquid and neutralizing acidified seawater, the hydrogen is used for reacting with the obtained bromine to prepare hydrobromic acid, and the obtained chlorine is used for chlorination or/and acidified chlorination distillation in the bromine extraction step; the hydrogen chloride gas synthesized by the hydrogen and chlorine is used for acidification or/and acidification chlorination distillation in the bromine extraction step. The invention can reduce the bromine production cost and avoid the problem of salt pollution in the surrounding sea area caused by directly discharging the concentrated seawater into the sea.
Description
Technical Field
The invention relates to a concentrated seawater utilization method for seawater desalination discharge, in particular to a method for comprehensively utilizing concentrated seawater, which can reduce bromine preparation cost and avoid sea area salt pollution.
Background
The chemical resources dissolved in the seawater comprise NaCl, bromide ions and the like, and the content of the NaCl is the highest and accounts for about 70 percent. The seawater desalination mainly adopts a reverse osmosis technology, and can generate a large amount of concentrated seawater with high salt content besides fresh water.
Bromine has been widely used as an important chemical raw material, and it is common to extract bromine from bromine-containing brine (such as seawater) by air blowing, including the processes of acidification, oxidation, blowing, absorption, distillation, etc. of seawater. Firstly, acidifying seawater by sulfuric acid or hydrochloric acid and the like, oxidizing the seawater by using chlorine to replace bromide ions to form elemental bromine, then spraying the acidified and oxidized seawater from the upper part of a blow-off tower, blowing air into the blow-off tower from the bottom of the blow-off tower, desorbing bromine in a packed tower by using the air to form bromine-containing gas and acidified seawater, and neutralizing the acidified seawater by using alkali liquor and then discharging the acidified seawater; inputting bromine-containing air into an absorption tower, and absorbing free hydrobromic acid by using absorbents such as sulfur dioxide or alkali liquor to obtain a finished solution so as to realize the enrichment of bromine; and finally, hydrochloric acid, chlorine and the like are used for acidifying, chlorinating and distilling the finished solution to obtain a bromine product, and the waste acid solution generated by distillation can be used for acidifying again. Besides natural seawater, a large amount of acid, chlorine, alkali liquor and the like are needed, and the production cost of bromine is increased.
Because the salt content of the concentrated seawater is very high, such as after the concentrated seawater is taken as a raw material and bromine in the concentrated seawater is extracted by adopting an air blowing method according to the prior art, the salt content of the generated acidic seawater still cannot be removed, so the method adopted by the seawater desalination enterprises at present is to directly discharge the concentrated seawater into the sea to cause salt pollution of the surrounding sea areas, and therefore, the development of the seawater desalination industry is also limited.
Disclosure of Invention
The invention aims to solve the technical problems in the prior art and provides a method for comprehensively utilizing concentrated seawater, which can reduce bromine preparation cost and avoid sea salt pollution.
The technical solution of the invention is as follows: a method for comprehensively utilizing concentrated seawater is characterized by comprising the following steps:
a. using concentrated seawater as a raw material, carrying out acidification, chlorination, air blowing and absorption to form a finished solution, carrying out acidification, chlorination and distillation on the finished solution to obtain a bromine finished product, and using distilled waste acid liquor for an acidification process;
b. neutralizing acidic seawater generated after air is blown out, and then performing ultrafiltration and electrodialysis concentration to prepare fresh seawater and strong brine, wherein the fresh seawater is discharged;
c. evaporating and crystallizing strong brine to obtain a refined salt finished product, carrying out flash evaporation crystallization on mother liquor obtained by crystallization to obtain a food-grade low-sodium salt finished product and waste liquor, and mixing the waste liquor with strong seawater for the step a; electrolyzing the refined salinized salt to obtain liquid alkali, hydrogen and chlorine; the obtained liquid alkali is used for absorption in the step a or/and neutralization in acidic seawater in the step b, the obtained hydrogen is used for reacting with bromine obtained in the step a to prepare hydrobromic acid, and the obtained chlorine is used for chlorination or/and acidification chlorination distillation in the step a; and (b) synthesizing hydrogen chloride gas by using the obtained hydrogen and chlorine for acidification or/and acidification chlorination distillation in the step a.
The invention takes concentrated seawater as raw material to extract bromine for production, acidic seawater generated in the bromine extraction process is neutralized by alkali liquor and then is subjected to ultrafiltration, electrodialysis concentration and other processes to obtain concentrated brine, the concentrated brine can be used for preparing refined salt and food-grade low sodium salt by adopting a salt preparation process, the refined salt can be electrolyzed to generate liquid alkali, hydrogen and chlorine, the liquid alkali can be used for blowing bromine absorption liquid and neutralizing acidified seawater, the hydrogen can be used for synthesizing hydrogen chloride with chlorine for acidification in the bromine extraction process, meanwhile, the hydrogen can be directly synthesized into hydrobromic acid with bromine, and the chlorine can be used for chlorination and acidification chlorination distillation in the bromine extraction process. The invention can reduce the bromine production cost and avoid the problem of salt pollution in the surrounding sea area caused by directly discharging the concentrated seawater into the sea.
Drawings
FIG. 1 is a flow chart of an embodiment of the present invention.
Detailed Description
The comprehensive utilization method of the concentrated seawater is shown in figure 1 and comprises the following steps:
a. extracting bromine by taking concentrated seawater as a raw material according to the existing air blowing method, namely forming a finished solution after acidification, chlorination, air blowing and absorption, carrying out acidification, chlorination and distillation on the finished solution to obtain bromine, and using distilled waste acid liquor for an acidification process; during initial production, the externally purchased hydrochloric acid or sulfuric acid can be used for acidification, and externally purchased alkali liquor is used for absorption;
b. neutralizing acidic seawater generated after air is blown out by alkali liquor, and concentrating by ultrafiltration (ceramic membrane) and electrodialysis to obtain fresh seawater and strong brine (containing about 200g/l of sodium chloride), wherein the fresh seawater is discharged, and the alkali liquor used in the initial production is purchased; the seawater can be deeply concentrated by ultrafiltration and electrodialysis concentration, and the inorganic salts in the concentrated seawater are mainly sodium chloride and potassium chloride, so that the method is very suitable for producing high-purity food-grade refined salt.
c. Evaporating and crystallizing the obtained strong brine to prepare refined salt with the purity of 99.9 percent, carrying out flash evaporation crystallization on mother liquor obtained by crystallization to prepare food-grade low-sodium salt and waste liquor, and mixing the waste liquor with concentrated seawater for extracting bromine in the step a; electrolyzing the refined salinized salt to obtain liquid alkali, hydrogen and chlorine, wherein the obtained liquid alkali is used for absorption in the step a or/and neutralization of acidic seawater in the step b, the obtained hydrogen is used for reacting with bromine obtained in the step a to prepare hydrobromic acid, and the obtained chlorine is used for chlorination or/and acidification chlorination distillation in the step a; and (b) synthesizing hydrogen chloride gas by using the obtained hydrogen and chlorine for acidification or/and acidification chlorination distillation in the step a.
Claims (1)
1. A method for comprehensively utilizing concentrated seawater is characterized by comprising the following steps:
a. using concentrated seawater as a raw material, carrying out acidification, chlorination, air blowing and absorption to form a finished solution, carrying out acidification, chlorination and distillation on the finished solution to obtain a bromine finished product, and using distilled waste acid liquor for an acidification process;
b. neutralizing acidic seawater generated after air is blown out, and then performing ultrafiltration and electrodialysis concentration to prepare fresh seawater and strong brine, wherein the fresh seawater is discharged;
c. evaporating and crystallizing strong brine to obtain a refined salt finished product, carrying out flash evaporation crystallization on mother liquor obtained by crystallization to obtain a food-grade low-sodium salt finished product and waste liquor, and mixing the waste liquor with strong seawater for the step a; electrolyzing the refined salinized salt to obtain liquid alkali, hydrogen and chlorine; the obtained liquid alkali is used for absorption in the step a or/and neutralization in acidic seawater in the step b, the obtained hydrogen is used for reacting with bromine obtained in the step a to prepare hydrobromic acid, and the obtained chlorine is used for chlorination or/and acidification chlorination distillation in the step a; and (b) synthesizing hydrogen chloride gas by using the obtained hydrogen and chlorine for acidification or/and acidification chlorination distillation in the step a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010428956.7A CN111573955A (en) | 2020-05-20 | 2020-05-20 | Comprehensive utilization method of concentrated seawater |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010428956.7A CN111573955A (en) | 2020-05-20 | 2020-05-20 | Comprehensive utilization method of concentrated seawater |
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| CN111573955A true CN111573955A (en) | 2020-08-25 |
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| CN202010428956.7A Pending CN111573955A (en) | 2020-05-20 | 2020-05-20 | Comprehensive utilization method of concentrated seawater |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB523607A (en) * | 1939-01-09 | 1940-07-18 | Dow Chemical Co | Improvements in or relating to the extraction of bromine |
| US4180547A (en) * | 1977-11-25 | 1979-12-25 | Ecodyne | Process for recovery of chemicals from saline water |
| CN101045529A (en) * | 2007-04-24 | 2007-10-03 | 天津长芦海晶集团有限公司 | Technology process for producing bromide using concentrated seawater |
| CN104276543A (en) * | 2013-07-02 | 2015-01-14 | 东营港湾石化有限公司 | New process for extracting bromine from concentrated seawater |
| CN106829866A (en) * | 2017-03-31 | 2017-06-13 | 四川永祥股份有限公司 | The technique that a kind of use bittern produces hydrochloric acid |
| CN108821238A (en) * | 2018-07-26 | 2018-11-16 | 崔斌德 | Blow out absorption process hydrobromic acid production method |
-
2020
- 2020-05-20 CN CN202010428956.7A patent/CN111573955A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB523607A (en) * | 1939-01-09 | 1940-07-18 | Dow Chemical Co | Improvements in or relating to the extraction of bromine |
| US4180547A (en) * | 1977-11-25 | 1979-12-25 | Ecodyne | Process for recovery of chemicals from saline water |
| CN101045529A (en) * | 2007-04-24 | 2007-10-03 | 天津长芦海晶集团有限公司 | Technology process for producing bromide using concentrated seawater |
| CN104276543A (en) * | 2013-07-02 | 2015-01-14 | 东营港湾石化有限公司 | New process for extracting bromine from concentrated seawater |
| CN106829866A (en) * | 2017-03-31 | 2017-06-13 | 四川永祥股份有限公司 | The technique that a kind of use bittern produces hydrochloric acid |
| CN108821238A (en) * | 2018-07-26 | 2018-11-16 | 崔斌德 | Blow out absorption process hydrobromic acid production method |
Non-Patent Citations (1)
| Title |
|---|
| 石洪源: "《海水资源利用产业发展现状与前景研究》", 31 July 2018, 广东经济出版社 * |
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