CN203922755U - Brine desulfuration system - Google Patents
Brine desulfuration system Download PDFInfo
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- CN203922755U CN203922755U CN201420269803.2U CN201420269803U CN203922755U CN 203922755 U CN203922755 U CN 203922755U CN 201420269803 U CN201420269803 U CN 201420269803U CN 203922755 U CN203922755 U CN 203922755U
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- inorganic ceramic
- brine
- ceramic film
- film filter
- reaction container
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Abstract
The utility model relates to a kind of brine desulfuration system, comprise the baffling groove connecting successively by pipeline, the first reaction container, coarse filter, the first inorganic ceramic film filter set, pretreatment system, tank before film, nanofiltration membrane separation device, the second reaction container and the second inorganic ceramic film filter set, nanofiltration membrane separation device is also connected with freezing and crystallizing device, freezing and crystallizing device is connected with dehydration by evaporation drying installation, freezing and crystallizing device also connects the second reaction container, the utility model brine desulfuration system, combine by physics and chemistry method, not only can make highly purified purification salt, can also process the high glass gall at self product place, both reduced environmental pollution, by waste liquid, give up and admittedly processed, and turn waste into wealth, the anhydrous sodium sulphate that sodium sulphate type bittern is made and high-quality salt solution, really reach zero disposal of pollutants.
Description
Technical field
The utility model relates to brine desulfuration field, relates in particular to a kind of brine desulfuration system and method thereof.
Background technology
In bittern, contain sodium sulfate impurity, for salt manufacturing, can affect with sodium-chlor eutectoid the purity of salt; For alkaline, sulfate radical can enter into ionic membrane, stops up film, affects service efficiency and the life-span of film.
In salt industry, sodium sulphate type bittern major impurity is that sodium sulfate (being about 15～30g/L) generally adopts multiple-effect evaporation technique to be prepared thenardite; Carry out salt, nitre by the coproduction of multiple-effect evaporation+sal prunella and separate, by-product saltcake when salt manufacturing, minority adopts cold method to remove sodium sulfate to prepare liquid salt, and because sodium sulfate concentration is low, freezing energy consumption is high and eliminated by enterprise gradually.
At chlor-alkali industry, along with popularizing of ionic membrane alkali making technology, liquid salt purity is more and more outstanding to the restriction of ionic membrane alkaline, and the enrichment of sulfate anion in brine system is the important factor that affects at present ionic membrane economic benefit.The major cause of bringing into of sulfate radical is that after raw materials for production containing sulfate radicals and electrolysis, salt solution uses chemical dechlorination to add reductive agent S-WAT, produces sulfate radical.Although embrane method denitration and other chemical process denitrations have obvious advantage, and the application percentage at chlor-alkali industry is increasing, the low glass gall of institute's output, not only sulfate radical content is low, and do not bring other impurity atoies into, and working cost, cost of investment etc. are all lower; But the high glass gall of embrane method output is without market using value.Most of chlor-alkali enterprises is deposited to reduce high nitre mother liquor and is arranged the pollution to environment outward by the freezing ten water nitre of making.
There is following technical problem in above-mentioned technique: (1). the multiple-effect evaporation sal prunella coproduction of salt industry, and the method for separating sodium sulfate, the purity of the sodium sulfate making is relatively low; (2). nanofiltration desulfurization, produce approximately 15% high-content sodium sulfate bittern without good whereabouts, even if adopt the freezing ten water nitre that make, but because ten water nitre are not the finished product, useless solid environmental pollution still has a certain impact.
The sodium sulfate purity that uses hot method desulfurization to make is separately low, in 98% left and right, can only reach the requirement of GB II class product; Using separately cold process can only make ten water nitre, is not the finished product, there is no marketable value, brings burden to environmental protection; Embrane method denitration separately, the high glass gall of output does not have place to go; And using separately chemical process desulfurization, expense is too high, and a large amount of salt slurry has greater environmental impacts.
Utility model content
The technical problems to be solved in the utility model is: in order to address the above problem, the utility model provides a kind of brine desulfuration system and method thereof.
The utility model solves the technical scheme that its technical problem adopts: a kind of brine desulfuration system, comprises tank before the baffling groove that connects successively by pipeline, the first reaction container, coarse filter, the first inorganic ceramic film filter set, pretreatment system, film, nanofiltration membrane separation device, the second reaction container and the second inorganic ceramic film filter set;
Described nanofiltration membrane separation utensil has two outlets, be respectively light outlet mutually and concentrated phase outlet, described the second retort is to be connected with the mouth that fades out of described nanofiltration membrane separation device, the concentrated phase outlet of described nanofiltration membrane separation device is connected with freezing and crystallizing device, described freezing and crystallizing utensil has crystallization outlet and brine outlet, described crystallization outlet is connected with dehydration by evaporation drying installation, and described brine outlet is connected with described the second reaction container.
Sometimes the silt content in bittern is too high, need to repeat to filter, further, the dense slime water being also provided with between described coarse filter and the first inorganic ceramic film filter set after the first inorganic ceramic film filter set can being filtered repeats the circulation tank through the first inorganic ceramic film filter set.
More consummate for the salt solution that makes finally to obtain, further, described pretreatment system comprises the static mixer, acid-regulating tank, activated carbon tower and the cartridge filter that connect successively by pipeline.
Specifically, the first described purpose ceramic-film filter group comprises three the first inorganic ceramic film filters that connect successively, the first inorganic ceramic film filter foremost connects the outlet of circulation tank, the first inorganic ceramic film filter of least significant end connects circulation tank entrance, and each the first inorganic ceramic film filter is all connected with static mixer.
Adopt above-mentioned brine desulfuration system to carry out the method for brine desulfuration, comprise that step is as follows,
Step 1: will contain CaSO
4, MgSO
4pump in baffling groove in the bittern of impurity, in baffling groove, adding concentration is the Na that 30% NaOH and concentration are 98%
2cO
3after pump in the first reaction container and react, remove the Ca in former halogen
2+and Mg
2+; Reacted bittern, after coarse filter filters, is pumped into the first inorganic ceramic film filter set and filters;
As preferably, the dosage of NaOH: preferably according to Mg
2+required molar weight conversion needs the amount of the NaOH consuming, after amount 0.1-0.3g/L,
Na
2cO
3dosage: preferably according to Ca
2+required molar weight conversion needs the Na consuming
2cO
3amount, after amount 0.2-0.4g/L,
In order to make the Ca in bittern
2+and Mg
2+remove more thoroughly, need to add excessive Na
2cO
3and NaOH, if but add-on too much can consume a large amount of alkali, and cost improves; Add-on is too low, can cause bittern pH to decline, thereby the magnesium hydroxide and the precipitation of calcium carbonate solubility product that form are uprised, and calcium in solution, magnesium ion are just relatively high and cannot eliminate, and therefore need strictly to control Na
2cO
3add-on with NaOH.
Step 2: the bittern after filtration enters tank before film after pretreatment system, tank is assigned to pretreated bittern in nanofiltration membrane separation device, to carry out separating sodium sulfate before film, low glass gall after separation enters in the second reaction container, high glass gall after separation pumps into freezing and crystallizing device, the ten water nitre slurries that crystallize out make anhydrous nitre through dehydration by evaporation drying installations, by the physical partition method of film and freezing+hot method, can removal system in 96% sodium sulfate, make anhydrous sodium sulphate product
Step 3: the chilled brine that freezing and crystallizing device produces also enters in the second reaction container, and adding concentration in the second reaction container is 22% bariumchloride (BaCL
2) react, remove the SO in bittern
4 2-; Reacted salt solution pumps into the second inorganic ceramic film filter set and filters, and obtains purification salt.
BaCL
2dosage: preferably according to SO
4 2-required molar weight conversion needs the BaCL consuming
2amount 94%, guarantee like this BaCL
2inexcessive, remaining Ba in minimizing system
2+on follow-up impact.
Further, the dense slime water after the first inorganic ceramic film filter set is filtered in step 1 can repeat to filter by circulation tank.
Particularly, the bittern after filtering is comprised and carries out static mixer to add concentration be to adjust pH value 5-7, activated carbon tower to adsorb in 31% mixed in hydrochloric acid, acid-regulating tank and the filtration of ensuring public security through the step of pretreatment system processing in step 2.Contain certain alkali number of crossing from purpose ceramic-film filter salt solution out, alkaline, regulate its potential of hydrogen by hydrochloric acid, the pH value of salt solution is adjusted to 5-7 by alkalescence, this is the requirement of nanofiltration membrane to salt solution, because of the different electric charge differences that can make the demonstration of material in solution of pH value, thereby the coulombic interaction on material and film surface is changed, can make the aggravation of concentration polarization phenomenon, make nanofiltration membrane flux reduce and ratio of desalinization decline, the wherein addition of hydrochloric acid: according to the amount of how many moles that the cross alkali number hydrochloric acid that consume that convert simultaneously.
The beneficial effects of the utility model are, the utility model brine desulfuration system and method thereof, (1) technique such as integrated use film, freezing, evaporation denitration and membrane filtration is carried out solventing-out to sodium sulfate in the brine, and the chilled brine of separation goes back to liquid salt workshop, anhydrous nitre packaging warehouse-in; Sodium sulfate in the refined brine making can be lower than 0.05g/L, and the refining anhydrous sodium sulphate purity making is more than 99.4%.
(2) the utility model can be avoided the shortcoming and defect of traditional method, is used in conjunction with by embrane method device, and it is main adopting physical desulfurization, and chemical method is auxiliary, effectively provide cost savings, and good economy performance, comprehensive energy consumption is low, and quality product is high, and environmentally safe.
Brief description of the drawings
Below in conjunction with drawings and Examples, the utility model is further illustrated.
Fig. 1 is the structured flowchart of the utility model brine desulfuration system and method thereof.
Embodiment
By reference to the accompanying drawings the utility model is described in further detail now.These accompanying drawings are the schematic diagram of simplification, and basic structure of the present utility model is only described in a schematic way, and therefore it only shows the formation relevant with the utility model.
As shown in Figure 1, comprise tank before the baffling groove that connects successively by pipeline, the first reaction container, coarse filter, the first inorganic ceramic film filter set, pretreatment system, film, nanofiltration membrane separation device, the second reaction container and the second inorganic ceramic film filter set;
Described nanofiltration membrane separation utensil has two outlets, be respectively light outlet mutually and concentrated phase outlet, described the second retort is to be connected with the mouth that fades out of described nanofiltration membrane separation device, the concentrated phase outlet of described nanofiltration membrane separation device is connected with freezing and crystallizing device, described freezing and crystallizing utensil has crystallization outlet and brine outlet, described crystallization outlet is connected with dehydration by evaporation drying installation, and described brine outlet is connected with described the second reaction container.Further, between coarse filter and the first inorganic ceramic film filter set, be also provided with and the dense slime water after the first inorganic ceramic film filter set is filtered can be repeated to the circulation tank through the first inorganic ceramic film filter set, wherein said pretreatment system comprises the static mixer connecting successively by pipeline, acid-regulating tank, activated carbon tower and cartridge filter, the first inorganic ceramic film filter set comprises three the first inorganic ceramic film filters that connect successively, the first inorganic ceramic film filter foremost connects the outlet of circulation tank, the first inorganic ceramic film filter of least significant end connects circulation tank entrance, each the first inorganic ceramic film filter is all connected with static mixer.
Embodiment 1
Adopt brine desulfuration system to carry out a method for brine desulfuration, comprise that step is as follows,
Step 1: will contain CaSO
4, MgSO
4deng bittern (NaCL300g/L, the Ca of impurity
2+0.65g/L, Mg
2+0.02g/L; SO
4 2-10g/L), in baffling groove, add the NaOH of 0.15g/L and the Na of 2.0g/L
2cO
3after pump in the first reaction container and react, remove the Ca in former halogen
2+and Mg
2+, reacted bittern, after coarse filter filters, is pumped into the first inorganic ceramic film filter set and filters.
Step 2: bittern (NaCL300g/L, Ca after filtration
2++ Mg
2+≤ 1mg/L; SO
4 2-10g/L) after pretreatment system, enter nanofiltration membrane separation device, flooding quantity is 100m
3/ h, the low glass gall (SO after separation
4 2-0.1g/L, flow 86m
3/ h), enter in the second reaction container the high glass gall (SO after separation
4 2-70g/L, flow 14m
3/ h) pumping into freezing and crystallizing device, the ten water nitre slurries that crystallize out make anhydrous nitre, the chilled brine (SO that freezing and crystallizing device produces after pervaporation, thickener thickening, centrifuge dewatering and drying bed are dry
4 2-4g/L) enter in the second reaction container, above-mentioned bittern after filtering is comprised and carries out static mixer to add concentration be 31% mixed in hydrochloric acid through the step of pretreatment system processing, hydrochloric acid add-on is in 0.42g/L, acid-regulating tank, to adjust pH value (5.5), and activated carbon tower adsorbs and the filtration of ensuring public security.
Step 3: adding concentration in the second reaction container is that 22% bariumchloride 1.30g/l reacts, and reacted salt solution pumps into the second inorganic ceramic film filter set and filters, and obtains purification salt (NaCL300g/L, Ca
2++ Mg
2+≤ 1mg/L; SO
4 2-0.045g/L).
The anhydrous sodium sulphate finally making: quality product reaches GB (GB6009-2003) I class acceptable end product standard.
Sodium sulfate (Na
2sO
4) 99.4%, water-insoluble 0.02%, calcium magnesium (in Mg) resultant 0.05%, muriate (in CL) 0.20%, iron (in Fe) 0.001%, moisture 0.01%, whiteness (R457) 86.
High-purity salt aquatic product quality detects as follows:
NaCL300g/L；Ca
2++Mg
2+0.05mg/L；SO
4 2-0.045g/L；SS0.5mg/L。
Embodiment 2
Adopt brine desulfuration system to carry out a method for brine desulfuration, comprise that step is as follows,
Step 1: will contain CaSO
4, MgSO
4deng bittern (NaCL290g/L, the Ca of impurity
2+0.85g/L, Mg
2+0.02g/L; SO
4 2-8g/L), in baffling groove, add the NaOH of 0.33g/L and the Na of 2.45g/L
2cO
3after pump in the first reaction container and react, remove the Ca in former halogen
2+and Mg
2+, reacted bittern, after coarse filter filters, is pumped into the first inorganic ceramic film filter set and filters.
Step 2: bittern (NaCL290g/L, Ca after filtration
2++ Mg
2+0.6mg/L; SO
4 2-8g/L) after pretreatment system, enter nanofiltration membrane separation device, flooding quantity is 150m
3/ h, the low glass gall (SO after separation
4 2-0.08g/L, flow 130m
3/ h), enter in the second reaction container the high glass gall (SO after separation
4 2-59.5g/L, flow 20m
3/ h) pumping into freezing and crystallizing device, the ten water nitre slurries that crystallize out make anhydrous nitre, the chilled brine (SO that freezing and crystallizing device produces after pervaporation, thickener thickening, centrifuge dewatering and drying bed are dry
4 2-4g/L) enter in the second reaction container, above-mentioned bittern after filtering is comprised and carries out static mixer to add concentration be to adjust pH value (7.0) in 31% mixed in hydrochloric acid 0.47g/L, acid-regulating tank through the step of pretreatment system processing, activated carbon tower adsorbs and the filtration of ensuring public security.
Step 3: adding concentration in the second reaction container is that 22% bariumchloride 1.22g/l reacts, and reacted salt solution pumps into the second inorganic ceramic film filter set and filters, and obtains purification salt (NaCL290g/L, Ca
2++ Mg
2+0.6mg/L; SO
4 2-0.042g/L).
The anhydrous sodium sulphate finally making: quality product reaches GB (GB6009-2003) I class acceptable end product standard.
Sodium sulfate (Na
2sO
4) 99.6%, water-insoluble 0.01%, calcium magnesium (in Mg) resultant 0.05%, muriate (in CL) 0.20%, iron (in Fe) 0.001%, moisture 0.008%, whiteness (R457) 88.
High-purity salt aquatic product quality detects as follows:
NaCL290g/L；Ca
2++Mg
2+0.6mg/L；SO
4 2-0.042g/L；SS0.5mg/L。
Embodiment 3
Adopt brine desulfuration system to carry out a method for brine desulfuration, comprise that step is as follows,
Step 1: will contain CaSO
4, MgSO
4deng bittern (NaCL300g/L, the Ca of impurity
2+0.4g/L, Mg
2+0.04g/L; SO
4 2-15g/L), in baffling groove, add the NaOH of 0.27g/L and the Na of 1.45g/L
2cO
3after pump in the first reaction container and react, remove the Ca in former halogen
2+and Mg
2+, reacted bittern, after coarse filter filters, is pumped into the first inorganic ceramic film filter set and filters.
Step 2: bittern (NaCL300g/L, Ca after filtration
2++ Mg
2+≤ 1mg/L; SO
4 2-15g/L) after pretreatment system, enter nanofiltration membrane separation device, flooding quantity is 80m
3/ h, the low glass gall (SO after separation
4 2-0.2g/L, flow 65m
3/ h), enter in the second reaction container the high glass gall (SO after separation
4 2-79g/L, flow 15m
3/ h) pumping into freezing and crystallizing device, the ten water nitre slurries that crystallize out make anhydrous nitre, the chilled brine (SO that freezing and crystallizing device produces after pervaporation, thickener thickening, centrifuge dewatering and drying bed are dry
4 2-3.5g/L) enter in the second reaction container, above-mentioned bittern after filtering is comprised and carries out static mixer to add concentration be to adjust pH value (6.0) in 31% mixed in hydrochloric acid 0.45g/l, acid-regulating tank through the step of pretreatment system processing, activated carbon tower adsorbs and the filtration of ensuring public security.
Step 3: adding concentration in the second reaction container is that 22% bariumchloride 1.68g/l reacts, and reacted salt solution pumps into the second inorganic ceramic film filter set and filters, and obtains purification salt (NaCL300g/L, Ca
2++ Mg
2+0.8mg/L; SO
4 2-0.049g/L).
The anhydrous sodium sulphate finally making: quality product reaches GB (GB6009-2003) I class acceptable end product standard.
Sodium sulfate (Na
2sO
4) 99.5%, water-insoluble 0.04%, calcium magnesium (in Mg) resultant 0.05%, muriate (in CL) 0.22%, iron (in Fe) 0.001%, moisture 0.009%, whiteness (R457) 87.
High-purity salt aquatic product quality detects as follows:
NaCL300g/L；Ca
2++Mg
2+0.8mg/L；SO
4 2-0.049g/L；SS0.5mg/L。
Taking above-mentioned foundation desirable embodiment of the present utility model as enlightenment, by above-mentioned description, relevant staff can, not departing from the scope of this utility model technological thought, carry out various change and amendment completely.The technical scope of this utility model is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (4)
1. a brine desulfuration system, is characterized in that: comprise tank before the baffling groove that connects successively by pipeline, the first reaction container, coarse filter, the first inorganic ceramic film filter set, pretreatment system, film, nanofiltration membrane separation device, the second reaction container and the second inorganic ceramic film filter set;
Described nanofiltration membrane separation utensil has two outlets, be respectively light outlet mutually and concentrated phase outlet, described the second retort is to be connected with the mouth that fades out of described nanofiltration membrane separation device, the concentrated phase outlet of described nanofiltration membrane separation device is connected with freezing and crystallizing device, described freezing and crystallizing utensil has crystallization outlet and brine outlet, described crystallization outlet is connected with dehydration by evaporation drying installation, and described brine outlet is connected with described the second reaction container.
2. brine desulfuration system as claimed in claim 1, is characterized in that: the dense slime water being also provided with between described coarse filter and the first inorganic ceramic film filter set after the first inorganic ceramic film filter set can being filtered repeats the circulation tank through the first inorganic ceramic film filter set.
3. brine desulfuration system as claimed in claim 1 or 2, is characterized in that: described pretreatment system comprises the static mixer, acid-regulating tank, activated carbon tower and the cartridge filter that connect successively by pipeline.
4. brine desulfuration system as claimed in claim 3, it is characterized in that: the first described purpose ceramic-film filter group comprises three the first inorganic ceramic film filters that connect successively, the first inorganic ceramic film filter foremost connects the outlet of circulation tank, the first inorganic ceramic film filter of least significant end connects circulation tank entrance, and each the first inorganic ceramic film filter is all connected with static mixer.
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|---|---|---|---|
| CN201420269803.2U CN203922755U (en) | 2014-05-23 | 2014-05-23 | Brine desulfuration system |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201420269803.2U CN203922755U (en) | 2014-05-23 | 2014-05-23 | Brine desulfuration system |
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| Publication Number | Publication Date |
|---|---|
| CN203922755U true CN203922755U (en) | 2014-11-05 |
Family
ID=51818611
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030319A (en) * | 2014-05-23 | 2014-09-10 | 中盐金坛盐化有限责任公司 | Brine desulphurization system and method |
| CN107879369A (en) * | 2016-09-29 | 2018-04-06 | 内蒙古乌海化工有限公司 | A kind of Waste Sulfuric Acid processing system and method |
-
2014
- 2014-05-23 CN CN201420269803.2U patent/CN203922755U/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104030319A (en) * | 2014-05-23 | 2014-09-10 | 中盐金坛盐化有限责任公司 | Brine desulphurization system and method |
| CN107879369A (en) * | 2016-09-29 | 2018-04-06 | 内蒙古乌海化工有限公司 | A kind of Waste Sulfuric Acid processing system and method |
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| GR01 | Patent grant |