CN102092880B - Process for freezing and denitriding primary brine with membrane method in polyvinyl chloride production - Google Patents
Process for freezing and denitriding primary brine with membrane method in polyvinyl chloride production Download PDFInfo
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- CN102092880B CN102092880B CN 201010568195 CN201010568195A CN102092880B CN 102092880 B CN102092880 B CN 102092880B CN 201010568195 CN201010568195 CN 201010568195 CN 201010568195 A CN201010568195 A CN 201010568195A CN 102092880 B CN102092880 B CN 102092880B
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- 238000000034 method Methods 0.000 title claims abstract description 71
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 29
- 239000012267 brine Substances 0.000 title claims abstract description 28
- 238000007710 freezing Methods 0.000 title claims abstract description 18
- 230000008014 freezing Effects 0.000 title claims abstract description 18
- 239000012528 membrane Substances 0.000 title abstract description 14
- 239000004800 polyvinyl chloride Substances 0.000 title abstract description 11
- 229920000915 polyvinyl chloride Polymers 0.000 title abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 12
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 106
- 150000003839 salts Chemical class 0.000 claims description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 55
- 239000011780 sodium chloride Substances 0.000 claims description 53
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 20
- 229910002651 NO3 Inorganic materials 0.000 claims description 19
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 19
- 239000012530 fluid Substances 0.000 claims description 14
- 230000000149 penetrating effect Effects 0.000 claims description 14
- 238000002425 crystallisation Methods 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000003507 refrigerant Substances 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 238000000053 physical method Methods 0.000 abstract description 2
- 239000002893 slag Substances 0.000 abstract description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 abstract 1
- 238000001728 nano-filtration Methods 0.000 abstract 1
- 230000001376 precipitating effect Effects 0.000 abstract 1
- 239000012716 precipitator Substances 0.000 abstract 1
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000003053 toxin Substances 0.000 abstract 1
- 231100000765 toxin Toxicity 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 7
- 229910001626 barium chloride Inorganic materials 0.000 description 7
- 229940045511 barium chloride Drugs 0.000 description 7
- 239000012266 salt solution Substances 0.000 description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000005484 gravity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
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- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a process for freezing and denitriding primary brine with a membrane method in polyvinyl chloride production, wherein a low-nitrite brine tank, a low-nitrite brine pump, a low-nitrite brine heat exchanger, a baffling groove, a concentrated-nitrite brine heat exchanger, a precipitator and a circulating pump are connected, and the purpose of treating sulfate radicals is achieved by firstly concentrating the sulfate radicals in the ionic-membrane light brine with a nano-filtration membrane method and then crystallizing and precipitating sodium sulfate decahydrate in the brine by adopting a freezing-method denitriding process. The process provided by the invention has the advantages of simplicity in operation, flexibility in treatment capacity and low operation cost, meanwhile, because sodium sulfate is separated from concentrated-nitrite brine by adopting a physical method and chemicals for removing the sulfate radicals do not need to be added, the environmental-protection effect of no toxin and harms and no discharging of waste liquid and slag is achieved, and moreover, the closed-loop circulation of the concentrated-nitrite brine can be realized so that no discharging of waste liquid is realized and pollution to the environment is prevented. The process can be widely applied to chlor-alkali production processes and is particularly suitable for the production process of vinyl chloride resin.
Description
Technical field
The present invention relates to the freezing technique of nitrate removal of embrane method of primary brine in a kind of embrane method freezing technique of nitrate removal, particularly polyvinyl chloride resin production of salt solution.
Background technology
In the production technique of polyvinyl chloride (PVC) RESINS, crude salt is one of its main raw material, needs raw material crude salt is dissolved as saturated brine and makes by filtering and impurity removing matter, a secondary refining in actual production to produce the processing requirement that gained salt solution reaches electrolysis with ion-exchange film.But due to the various zwitterions that exist in salt solution, if sulfate ion too high levels can the ionic membrane in follow-up electrolysis process be resulted in blockage particularly raises bath voltage, current efficiency descends, thereby affects normal electrolysis production, increases production cost.
Remove method domestic main employing barium chloride method sulfate radical at present for sulfate radical in actual production, namely use bariumchloride, sulfate radical is removed with the form of barium sulfate precipitate, because barium sulfate solubleness is low, remove the effective of sulfate radical, thereby become present topmost technique of nitrate removal.But the artificial factor impact of this method is larger, controls unstable to the removal effect of sulfate radical simultaneously.When in system, barium ion exceeds standard, can form insoluble complex with iodide ion, the ionic membrane effect is worsened, obviously affect its current efficiency and bath voltage.Secondly add if bariumchloride is excessive, move back to the original place of residence in the electric groove sodium hydroxide that moves on to the anolyte compartment of existence meeting is combined and is generated the hydrated barta precipitation again, is deposited on the life-span that shortens film on film, reduces current efficiency.Bariumchloride is poisonous simultaneously, human body and surrounding environment are also worked the mischief, and bariumchloride price more expensive (2700-3000 yuan/ton), along with the sulfate radical content in raw material salt raises, this method processing costs increases.Also have in addition calcium owned by France in chemical process, namely use calcium chloride, sulfate radical is carried out chemical reaction generate precipitation, removed with the form of gypsum.The relative barium method of this method working cost is low, but needs to add some equipment, and more complicated in operation is difficult to control stable.The resin rule is to make spent ion exchange resin, absorption exchange sulfate ion, and removal effect is good.Use the resin volume large but exist simultaneously, the required soda acid amount of resin regeneration and pure water consumption are large, move the shortcomings such as uneconomical.
At present more advanced method is the embrane method technique of nitrate removal, and the method has overcome the shortcoming of above-mentioned several techniques, has simultaneously environmental protection, advantages such as nontoxic, simple to operate, investment is little, instant effect, thereby is paid attention to.This method adopts Nanofiltering membrane first the sulfate radical in the ionic membrane light salt brine to be concentrated, then adopts the cold method technique of nitrate removal to make sal glauberi in salt solution as the product crystallization, reaches the purpose of processing sulfate radical, and the use of doing of recovered brine salt.This method is that environmental protection need not add bariumchloride again, has realized the purpose of zero release in the sulfate radical treatment process, is worthy of promotion and application in ion film caustic soda sulfate radical technique.Membrane process craft is divided into three parts: preprocessing part, film device part and freezing except the nitre part, wherein front two portions technique is very ripe, last freezing denitration part is due to the problem that can't resolve sulfate crystal in cooling apparatus always, affect the production of normal process, domestic each enterprise operation is immature at present, does not propose better terms of settlement.
Summary of the invention
the invention solves that in present polyvinyl chloride (PVC) RESINS industry production, required primary brine sulfate ion in the ionic membrane operation to be removed middle cost high, complex process, move uneconomical, the shortcomings such as work-ing life of ionic membrane can't be recycled and affect to by product, and then provide a kind of expense low, efficient is high, pollution-free, sulfate ion can be recycled as the method for product crystallization then with sal glauberi simultaneously, thereby can effectively reduce production costs, reduce and pollute, invest simultaneously little, simple and reasonable, the freezing technique of nitrate removal of embrane method of primary brine in a kind of polyvinyl chloride resin production of instant effect.
The method that cold method technique of nitrate removal provided by the present invention removes sulfate ion is to adopt Nanofiltering membrane first the sulfate radical in the ionic membrane light salt brine to be concentrated, adopt again the cold method technique of nitrate removal to make sal glauberi in salt solution as the product crystallization, reach the purpose of processing sulfate radical, adopting this method is that environmental protection need not add bariumchloride again, realized the purpose of zero release in the sulfate radical treatment process, be worthy of promotion and application in ion film caustic soda sulfate radical technique.
the technical scheme of this reality invention is: the freezing technique of nitrate removal of primary brine in described a kind of Production of PVC comprises connected low salt made from earth containing a comparatively high percentage of sodium chloride water pot, low salt made from earth containing a comparatively high percentage of sodium chloride water pump, low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger, baffling groove, dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger, settling vessel and recycle pump, comprise the steps: 1. to enter the baffling groove and to regulate the pH value to 7-11 from the concentrated solution of film device, then through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger circulation temperature lowering to 10～15 ℃, 2. at first the low nitre penetrating fluid from film device enters into low salt made from earth containing a comparatively high percentage of sodium chloride water pot when the tank liquid level reaches 2/3rds, open low salt made from earth containing a comparatively high percentage of sodium chloride water pump, after lowering the temperature, the interchanger that low nitre penetrating fluid is-8～-30 ℃ of refrigerated waters via refrigerant enters settling vessel, until clear liquid enters to hang down salt made from earth containing a comparatively high percentage of sodium chloride water pot three/two o'clock from settling vessel upper end overflow, stop adding low nitre penetrating fluid in tank, 3. the low nitre penetrating fluid in low salt made from earth containing a comparatively high percentage of sodium chloride water pot and settling vessel by low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger progressively circulation temperature lowering make in settling vessel temperature between-8～-15 ℃, then add 1. middle concentrated solution through cooling process of step by recycle pump in settling vessel, adopt the method for direct combination cooling that the sulfate crystal in concentrated solution is separated out, and in settling vessel natural subsidence, reach separating of salt and nitre, the low nitre penetrating fluid sodium sulphate content that overflows from settling vessel is controlled at and is not more than 15g/l, slurry from settling vessel bottom mass crystallization body out passes through the whizzer centrifugal treating at last, centrifuge mother liquor enters low salt made from earth containing a comparatively high percentage of sodium chloride water storage tank, sodium sulfate packing with crystal water is sent.
The freezing technique of nitrate removal of primary brine in described a kind of Production of PVC, its step 2. in circulation temperature lowering makes settling vessel temperature be-8～-15 ℃, the concentrated solution at this temperature be conducive to improve step 3. in crystalline rate; Step 3. in concentrated solution sodium sulfate crystallisation by cooling temperature be-5～-10 ℃.
The freezing technique of nitrate removal of primary brine in described a kind of Production of PVC, the low salt made from earth containing a comparatively high percentage of sodium chloride aqueous sodium persulfate content that the warp that its step overflows from settling vessel in is 3. processed except nitre is controlled at and is not more than 15g/l, and final step obtains sodium sulfate with crystal water from the slurry of settling vessel bottom mass crystallization body out through the whizzer centrifugal treating through natural subsidence in 2..
Advantage of the present invention.
the present invention is by first processing nano filter membrance device to the sulfate radical in the ionic membrane light salt brine, be divided into two strands of liquid: the low nitre penetrating fluid that the concentrated solution that sulfate radical content is high and sulfate radical content are low, the salt aquation salt system of returning low nitre penetrating fluid continues to use, concentrated solution enters freezing technique of nitrate removal, the solubleness under differing temps according to sodium sulfate and sodium-chlor, adopt a kind of rational Freeze crystallization method realization separation both, finally obtain product saltcake and the reuse that realizes sodium chloride solution, thereby can realize full automatic control on producing, simple to operate, treatment capacity is flexible, working cost is low, and solved the problem that tubular heat exchange in freezing technique of nitrate removal stops up continuously, guarantee production steady running, simultaneously owing to adopting physical method separating sodium sulfate from dense salt made from earth containing a comparatively high percentage of sodium chloride water, need not to add the sulfate radical medicament, reached nontoxic, environment protecting without liquid and waste slag produced discharging, and can accomplish the closed cycle of dense salt made from earth containing a comparatively high percentage of sodium chloride water, realize Zero discharge, avoid environment, reduce ton alkali salt consumption and the production cost of our unit, the present invention can be widely used in chlor-alkali production technique, be specially adapted in the production technique of polyvinyl chloride (PVC) RESINS.
Description of drawings
Fig. 1 is the embodiments of the invention process flow sheet;
In Fig. 1: 1 for the baffling groove, 2 for the concentrated solution storage tank, 3 for concentrated brine feed pump, 4 for dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger A, 5 for convert the halogen groove, 6 for for dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger B, 7 for recycle pump, 8 for settling vessel, 9 for low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger, 10 for low salt made from earth containing a comparatively high percentage of sodium chloride water pump, 11 for hanging down the salt made from earth containing a comparatively high percentage of sodium chloride water pot.
Embodiment
Embodiment: with reference to accompanying drawing, specific embodiments of the present invention is: the present embodiment comprises that the 1 baffling groove, 2 concentrated solution storage tanks, 3 concentrated brine feed pumps, the 4 dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger A, 5 that are connected successively convert halogen groove, 6 and are dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger B, 7 recycle pumps, 8 settling vessels, 9 low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchangers, 10 low salt made from earth containing a comparatively high percentage of sodium chloride water pumps, 11 low salt made from earth containing a comparatively high percentage of sodium chloride water pots.At first add the sodium hydroxide solution adjust pH to 7-11 through the baffling groove from film device concentrated solution out, then gravity flow enters in the concentrated solution storage tank, then pumps into dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger A by concentrated brine feed and cool to 20 ℃.Then gravity flow enters salt solution and converts the halogen groove; Extracted out from the bottom by recycle pump after mixing in converting the halogen groove again through the dense salt made from earth containing a comparatively high percentage of sodium chloride water after cooling once, through overrich salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger B circulation temperature lowering to 10 ℃.
Simultaneously when just driving, due to liquid (low nitre penetrating fluid) must be housed in the production technique device in advance, otherwise can't running gear, therefore must first allow film device low nitre penetrating fluid out enter into low salt made from earth containing a comparatively high percentage of sodium chloride water pot, then when the tank liquid level reaches 2/3rds, the low salt made from earth containing a comparatively high percentage of sodium chloride water pump of unlatching will hang down and enter settling vessel after salt made from earth containing a comparatively high percentage of sodium chloride water is sent into low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger cooling, until clear liquid enters to hang down in the salt made from earth containing a comparatively high percentage of sodium chloride water pot from settling vessel upper end overflow, at this moment stop adding low nitre penetrating fluid in tank.Liquid in this moment low salt made from earth containing a comparatively high percentage of sodium chloride water pot and settling vessel by row hang down nitre interchanger interchanger progressively circulation temperature lowering arrive-10 ℃, then add concentrated solution by recycle pump in settling vessel, method by direct combination cooling is separated out the sulfate crystal in concentrated solution, and in settling vessel natural subsidence, reach separating of salt and nitre, must guarantee in settling vessel temperature in this operating process between-5--10 ℃, the low salt made from earth containing a comparatively high percentage of sodium chloride aqueous sodium persulfate content that overflows from settling vessel is controlled at below 15g/l.
From the slurry process whizzer centrifugal treating of settling vessel bottom mass crystallization body out, centrifuge mother liquor enters low salt made from earth containing a comparatively high percentage of sodium chloride water storage tank, sends with the sodium sulfate packing of crystal water at last.
Another embodiment difference is that concentrated solution cools to 23 ℃ through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger A, then is cooled to 13 ℃ through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger B, and the interior temperature of settling vessel this moment is-8 ℃.
Another embodiment difference is that concentrated solution cools to 25 through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger A and is cooled to 15 ℃ through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger B, the time settling vessel in temperature be-10 ℃.
Above embodiment can require to carry out temperature according to concrete actual production and control.
Claims (5)
1. the freezing technique of nitrate removal of primary brine in a Production of PVC, is characterized in that comprising connected low salt made from earth containing a comparatively high percentage of sodium chloride water pot, low salt made from earth containing a comparatively high percentage of sodium chloride water pump, low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger, baffling groove, dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger, settling vessel and recycle pump, comprise the steps: 1. to enter the baffling groove and to regulate the pH value to 7-11 from the concentrated solution of film device, then through dense salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger circulation temperature lowering to 10～15 ℃, 2. at first the low nitre penetrating fluid from film device enters into low salt made from earth containing a comparatively high percentage of sodium chloride water pot when the tank liquid level reaches 2/3rds, open low salt made from earth containing a comparatively high percentage of sodium chloride water pump, after lowering the temperature, the interchanger that low nitre penetrating fluid is-8～-30 ℃ of refrigerated waters via refrigerant enters settling vessel, until clear liquid enters to hang down in the salt made from earth containing a comparatively high percentage of sodium chloride water pot from settling vessel upper end overflow, at this moment stop adding low salt made from earth containing a comparatively high percentage of sodium chloride water in tank, 3. the low nitre penetrating fluid in low salt made from earth containing a comparatively high percentage of sodium chloride water pot and settling vessel by low salt made from earth containing a comparatively high percentage of sodium chloride water-to-water heat exchanger progressively circulation temperature lowering make in settling vessel temperature between-8～-15 ℃, then add 1. middle concentrated solution through cooling process of step by recycle pump in settling vessel, adopt the method for direct combination cooling that the sulfate crystal in concentrated solution is separated out, and in settling vessel natural subsidence, reach separating of salt and nitre, the low nitre penetrating fluid sodium sulphate content that overflows from settling vessel is controlled at and is not more than 15g/L, slurry from settling vessel bottom mass crystallization body out passes through the whizzer centrifugal treating at last, centrifuge mother liquor enters low salt made from earth containing a comparatively high percentage of sodium chloride water storage tank, sodium sulfate packing with crystal water is sent.
2. the freezing technique of nitrate removal of primary brine in a kind of Production of PVC according to claim 1, it is characterized in that step 2. in circulation temperature lowering makes settling vessel temperature be-10～-15 ℃.
3. the freezing technique of nitrate removal of primary brine in a kind of Production of PVC according to claim 1 and 2 is characterized in that sodium sulfate crystallisation by cooling temperature is-5～-10 ℃ during step 3..
4. the freezing technique of nitrate removal of primary brine in a kind of Production of PVC according to claim 3, the low salt made from earth containing a comparatively high percentage of sodium chloride aqueous sodium persulfate content that the warp that it is characterized in that overflowing from settling vessel during step is 3. processed except nitre is controlled at and is not more than 8g/L.
5. the freezing technique of nitrate removal of primary brine in a kind of Production of PVC of stating according to claim 4 is characterized in that during step 2. obtaining sodium sulfate with crystal water from the slurry of settling vessel bottom mass crystallization body out through the whizzer centrifugal treating through natural subsidence.
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| CN104310659B (en) * | 2014-11-12 | 2016-06-01 | 福州大学 | Containing high density SO42-Percolate MBR+NF concentrated solution in humic acids process for separating and recovering |
| CN104803525B (en) * | 2014-12-10 | 2017-01-11 | 青岛和合汇途工程技术有限公司 | Method for processing high salinity wastewater and device thereof |
| CN104891704A (en) * | 2015-05-05 | 2015-09-09 | 岳嵩 | High-salt content waste water treatment method |
| CN109607654A (en) * | 2019-01-31 | 2019-04-12 | 内蒙古科技大学 | Device, method and the application of strong brine low temperature crystallization desalination |
| CN112321046A (en) * | 2020-09-24 | 2021-02-05 | 四川永祥股份有限公司 | Salt recovery system for light brine and concentrated mother liquor |
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| CN2908466Y (en) * | 2006-02-12 | 2007-06-06 | 山东滨化集团有限责任公司 | Concentration nano filtering, recovery device of magnesium sulfate solution |
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| CN101041444A (en) * | 2007-03-20 | 2007-09-26 | 山东布莱恩化工技术有限公司 | Method freezing separating mirabilite by brine solution |
| CN101544436A (en) * | 2009-05-08 | 2009-09-30 | 清华大学 | Method for removing and recovering sulfate in acrylonitrile wastewater by utilizing freezing crystallization |
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