CN101033072A - Method of preparing special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production - Google Patents
Method of preparing special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production Download PDFInfo
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- CN101033072A CN101033072A CN 200710014278 CN200710014278A CN101033072A CN 101033072 A CN101033072 A CN 101033072A CN 200710014278 CN200710014278 CN 200710014278 CN 200710014278 A CN200710014278 A CN 200710014278A CN 101033072 A CN101033072 A CN 101033072A
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Abstract
This invention relates to a method for preparing low bromine industrial salt with ionic film method chlorine alkali , in which, waste of alkali processed with ammonia-soda process is added in a first salt pool, the volume of which is 15-30t according to 150 thousand cubic meters of brine in said pool to be changed once a year and the mean flow rate each year is 50-70m3/h. The mean content of Mg ions is lower than 0.05%, SO4 is lower than 0.32%, and Ca: Mg is greater than 2.0, and bromine is not tested.
Description
Technical field the present invention relates to a kind of preparation method of Industrial Salt, and particularly a kind of ionic membrane method that adopts is produced in the chloralkali process preparation method as the special-purpose low-bromine industrial salt of raw material.
Background technology is utilized in the common crude salt (main component sodium-chlor) that current methods produces, and magnesium ion and sulfate radical content are higher, and on the other hand, calcium ion and magnesium ion content ratio are on the low side.Produce in the technology of chlor-alkali at ionic membrane method, this problem can cause the shortening in work-ing life of this expensive consumable material of ionic membrane, and then causes the raising of production cost and the reduction of production efficiency.
On the other hand, in the existing salt producing craft, have without carrying bromine, have only through once carrying bromine, have to put forward bromine technology reasonable inadequately, the result is that the content of bromine in the Industrial Salt finished product is higher, not only causes the waste of this expensive resource of bromine, and causes ionic membrane method to be produced in chloralkali process and the subsequent product because the too high quality problems that causes of bromine content.
Summary of the invention the objective of the invention is to overcome the deficiency of above-mentioned existing salt extraction process, and provide a kind of preparation method of special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production, technical problem to be solved is: by improving processing condition, make magnesium ion and sulfate radical content reduction in the crude salt, improve the content ratio of calcium ion and magnesium ion simultaneously.Second technical problem to be solved by this invention be, puies forward the processing condition of bromine by improving secondary, and it is stronger, more reasonable to make secondary put forward bromine technology specific aim, and the extraction yield of bromine is higher, and the brominated amount of Industrial Salt is lower.
The technical solution adopted in the present invention is as follows:
A kind of preparation method of special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production comprises the following steps of carrying out successively:
The first step: extract salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond;
It is characterized in that: in the 3rd step, add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by the first evaporation tank bittern, 15 ten thousand steres, add the 15-30 ton, the annual replacing once; In the pond bittern annual flow velocity the 50-70 cubic meter/hour.
Preferred version is: in the 3rd step, the waste material add-on is in the pond: by the first evaporation bittern, 15 ten thousand steres, add the 20--25 ton, the annual replacing once; In the pond bittern annual flow velocity the 60--65 cubic meter/hour.
Second step was decomposed into once carries bromine and secondary is carried bromine, wherein once carries bromine according to common process, and the secondary method for extracting bromine is as follows:
The 1st step: the bittern of once carrying behind the bromine flows into Buffer Pool naturally;
The 2nd step: utilize liquid pump that the bittern in the Buffer Pool is pumped into stripping tower through pipeline, add chlorine in the pipeline and make bromide anion oxidation in pipeline;
The 3rd step: bittern enters stripping tower from the top spray, utilizes blower fan upwards to be blown into air from blowing out tower bottom, free bromine in the bittern is parsed form the bromine air;
The 4th step: bromine air admission absorption tower, and add sulfurous gas and water, form hydrobromic acid mist;
The 5th step: hydrobromic acid mist distilled make bromine;
In the 3rd step, spray 1m
3The wind supply quantity of bittern is 140-180m
3The specific liquid rate of bittern is: 20--30m
3/ m
2, hour.
In the 4th step, the absorption tower is cut off and is divided into two absorption chambers, i.e. first absorption chamber and second absorption chamber, between two absorption chambers passage as the revolution mouth of bromine air, this passage is positioned at and cuts off the below; Flow through successively behind the bromine air admission absorption tower first absorption chamber, passage and second absorption chamber are discharged from the outlet of second absorption chamber upper end.
In the 4th step, sulfurous gas and water join respectively from two small transfer lines in first absorption chamber and second absorption chamber.
In the 2nd step, adding amount of chlorine in the pipeline is that benchmark is between 110--120% with brominated amount.
In the 4th step, the add-on of water makes the content of bromine in the absorption liquid at 30--50kg/m
3
The 5th the step in, chlorine dosage with brominated amount be benchmark between 105--110%, steam temperature is between 80--90 ℃.
Positively effect of the present invention is: (1), (mensuration of calcium and magnesium ion is according to GB/T13025.6-91 through conventional method.The mensuration of sulfate ion is according to GB/T 13025.8-91.) repeated detection, this special use Industrial Salt magnesium ion content on average is lower than 0.05%, and sulfate radical content on average is lower than 0.32%, and the calcium ions and magnesium ions ratio is on average greater than 2.0.And the magnesium ion content of top grade general industry salt national Specification is 0.15%, and sulfate radical content is 0.50%, and the calcium ions and magnesium ions ratio is more than or equal to 1.0.This shows that magnesium ion and sulfate radical content reduce significantly in the special-purpose Industrial Salt of the present invention, the content ratio of calcium ion and magnesium ion increases substantially simultaneously.Therefore, can obviously prolong the work-ing life of chlor-alkali production ionic membrane.(2), in the ammonia alkali legal system alkali waste material, muriatic existence reduces water-quality guideline, harm underground water and soil as long as air storage has strong breeze to fly upward by alkaline residue, cause Air quality to worsen suddenly.Therefore, the present invention has positive effect for solving alkaline residue this " white pollution ".(3), the crude salt overall target improves, quality is more excellent.(4), ShanghaiChlorine and Alkali Chemical Co Ltd's inspection report shows that it according to QG/Z0408-07 standard test result is: not carrying the bromine industrial salt bromine content is 119 microgram/grams, and finished product Industrial Salt of the present invention does not detect bromine.
Embodiment further specifies the present invention below in conjunction with specific embodiment.
Embodiment one
The first step: ordinary method extracts salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
Add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by first solarization salt pond bittern 15 ten thousand steres, add 15 tons, the annual replacing once; Bittern annual flow velocity is at 60 cubic metres/hour in the pond.
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond, and common process is evaporated brine.
Embodiment two
The first step: ordinary method extracts salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
Add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by through the first evaporation tank bittern, 15 ten thousand steres, add 25 tons, the annual replacing once; Bittern annual flow velocity is at 70 cubic metres/hour in the pond.
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond, and common process is evaporated brine.
Embodiment three
The first step: ordinary method extracts salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
Add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by the first evaporation tank bittern, 15 ten thousand steres, add 30 tons, the annual replacing once; Bittern annual flow velocity is at 50 cubic metres/hour in the pond.
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond, and common process is evaporated brine.
Embodiment four
The first step: ordinary method extracts salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
Add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by the first evaporation tank bittern, 15 ten thousand steres, add 20 tons, the annual replacing once; Bittern annual flow velocity is at 65 cubic metres/hour in the pond.
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond, and common process is evaporated brine.
This first bittern amount of flowing through of shining the salt pond is the annual flow that can produce about 8000 tons of salt.
Wherein, the waste material of ammonia alkali legal system alkali is sample examination repeatedly, and it is as follows to record component content: calcium chloride 50-60%, and calcium hydroxide: 10-15%, calcium oxide 5-10%, all the other are impurity such as water, sodium-chlor and lime carbonate.
Embodiment five
Other step is decomposed into embodiment one, the second step and once carries bromine and secondary is carried bromine, wherein once carries bromine according to common process, and the secondary method for extracting bromine is as follows:
The 1st step: the bittern of once carrying behind the bromine flows into Buffer Pool naturally;
The 2nd step: utilize liquid pump that the bittern in the Buffer Pool is pumped into stripping tower through pipeline, add chlorine in the pipeline and make bromide anion oxidation in pipeline;
The 3rd step: bittern enters stripping tower from the top spray, utilizes the white stripping tower of blower fan bottom upwards to be blown into air, free bromine in the bittern is parsed form the bromine air;
The 4th step: bromine air admission absorption tower, and add sulfurous gas and water, form hydrobromic acid mist;
The 5th step: hydrobromic acid mist distilled make bromine;
Wherein, in the 3rd step, spray 1m
3The wind supply quantity of bittern is 140-160m
3The specific liquid rate of bittern is: 20--25m
3/ m
2, hour.
In the 4th step, the absorption tower is cut off and is divided into two absorption chambers, i.e. first absorption chamber and second absorption chamber, between two absorption chambers passage as the revolution mouth of bromine air, this passage is positioned at and cuts off the below; Flow through successively behind the bromine air admission absorption tower first absorption chamber, passage and second absorption chamber are discharged from the outlet of second absorption chamber upper end.
In the 4th step, sulfurous gas and water join respectively from two small transfer lines in first absorption chamber and second absorption chamber.
In the 2nd step, adding amount of chlorine in the pipeline is that benchmark is between 110--120% with brominated amount.
In the 4th step, the add-on of water makes the content of bromine in the absorption liquid at 30--50kg/m
3
The 5th the step in, chlorine dosage with brominated amount be benchmark between 105--110%, steam temperature is between 80--90 ℃.
Claims (3)
1, a kind of preparation method of special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production comprises the following steps of carrying out successively:
The first step: extract salt manufacturing bittern;
Second step: from bittern, carry bromine;
The 3rd step: second step was carried behind the bromine bittern first evaporation tank of flowing through;
The 4th step: the bittern after the 3rd step handled enters the subsequent evaporation pond and shines the salt pond;
It is characterized in that: in the 3rd step, add the waste material of ammonia alkali legal system alkali in the pond, add-on is: by the first evaporation tank bittern, 15 ten thousand steres, add the 15-30 ton, the annual replacing once; In the pond bittern annual flow velocity the 50-70 cubic meter/hour.
2, the preparation method of special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production as claimed in claim 1 is characterized in that: in the 3rd step, the waste material add-on is in the pond: by the first evaporation tank bittern, 15 ten thousand steres, add the 20--25 ton, the annual replacing once; In the pond bittern annual flow velocity the 60--65 cubic meter/hour.
3, the preparation method of special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production as claimed in claim 1 or 2 is characterized in that: second step was decomposed into once carries bromine and secondary is carried bromine, wherein once carries bromine according to common process, and the secondary method for extracting bromine is as follows:
The 1st step: the bittern of once carrying behind the bromine flows into Buffer Pool naturally;
The 2nd step: utilize liquid pump that the bittern in the Buffer Pool is pumped into stripping tower through pipeline, add chlorine in the pipeline and make bromide anion oxidation in pipeline;
The 3rd step: bittern enters stripping tower from the top spray, utilizes blower fan upwards to be blown into air from blowing out tower bottom, free bromine in the bittern is parsed form the bromine air;
The 4th step: bromine air admission absorption tower, and add sulfurous gas and water, form hydrobromic acid mist;
The 5th step: hydrobromic acid mist distilled make bromine;
In the 3rd step, spray 1m
3The wind supply quantity of bittern is 140-180m
3The specific liquid rate of bittern is: 20--30m
3/ m
2, hour.
In the 4th step, the absorption tower is cut off and is divided into two absorption chambers, i.e. first absorption chamber and second absorption chamber, between two absorption chambers passage as the revolution mouth of bromine air, this passage is positioned at and cuts off the below; Flow through successively behind the bromine air admission absorption tower first absorption chamber, passage and second absorption chamber are discharged from the outlet of second absorption chamber upper end.
In the 4th step, sulfurous gas and water join respectively from two small transfer lines in first absorption chamber and second absorption chamber.
In the 2nd step, adding amount of chlorine in the pipeline is that benchmark is between 110--120% with brominated amount.
In the 4th step, the add-on of water makes the content of bromine in the absorption liquid at 30--50kg/m
3
The 5th the step in, chlorine dosage with brominated amount be benchmark between 105--110%, steam temperature is between 80--90 ℃.
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CNB2007100142784A CN100494062C (en) | 2007-04-11 | 2007-04-11 | Method of preparing special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production |
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CNB2007100142784A CN100494062C (en) | 2007-04-11 | 2007-04-11 | Method of preparing special-purpose low-bromine industrial salt for ionic membrane method alkali-chloride production |
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CN100494062C CN100494062C (en) | 2009-06-03 |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105600753A (en) * | 2015-12-30 | 2016-05-25 | 山东昌邑廒里盐化有限公司 | Method for extracting bromine from brine |
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2007
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105600753A (en) * | 2015-12-30 | 2016-05-25 | 山东昌邑廒里盐化有限公司 | Method for extracting bromine from brine |
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