CN115385496A - Recovery system and method for waste liquid produced by ammonium nitrate exchange molecular sieve - Google Patents
Recovery system and method for waste liquid produced by ammonium nitrate exchange molecular sieve Download PDFInfo
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- CN115385496A CN115385496A CN202211042019.3A CN202211042019A CN115385496A CN 115385496 A CN115385496 A CN 115385496A CN 202211042019 A CN202211042019 A CN 202211042019A CN 115385496 A CN115385496 A CN 115385496A
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- 239000007788 liquid Substances 0.000 title claims abstract description 39
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical group OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000011084 recovery Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 23
- 239000012528 membrane Substances 0.000 claims abstract description 111
- 239000000243 solution Substances 0.000 claims abstract description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 238000000909 electrodialysis Methods 0.000 claims abstract description 21
- 239000000919 ceramic Substances 0.000 claims abstract description 20
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 17
- 150000002500 ions Chemical class 0.000 claims abstract description 14
- 239000012510 hollow fiber Substances 0.000 claims abstract description 13
- 238000010521 absorption reaction Methods 0.000 claims abstract description 11
- 239000012535 impurity Substances 0.000 claims abstract description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007872 degassing Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000003513 alkali Substances 0.000 claims description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims description 18
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 238000005342 ion exchange Methods 0.000 claims description 12
- 230000009615 deamination Effects 0.000 claims description 10
- 238000006481 deamination reaction Methods 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- -1 ammonium ions Chemical class 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- FGHSTPNOXKDLKU-UHFFFAOYSA-N nitric acid;hydrate Chemical compound O.O[N+]([O-])=O FGHSTPNOXKDLKU-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 230000003139 buffering effect Effects 0.000 claims description 4
- 229910001424 calcium ion Inorganic materials 0.000 claims description 4
- 238000005341 cation exchange Methods 0.000 claims description 4
- 230000005684 electric field Effects 0.000 claims description 4
- 229910001425 magnesium ion Inorganic materials 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- 239000001099 ammonium carbonate Substances 0.000 claims description 3
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 230000009466 transformation Effects 0.000 claims description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 14
- 239000002351 wastewater Substances 0.000 abstract description 8
- 239000012266 salt solution Substances 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 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 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 238000005406 washing Methods 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
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- 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
- C02F1/20—Treatment of water, waste water, or sewage by degassing, i.e. liberation of dissolved gases
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/16—Nitrogen compounds, e.g. ammonia
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/46—Apparatus for electrochemical processes
- C02F2201/461—Electrolysis apparatus
- C02F2201/46105—Details relating to the electrolytic devices
- C02F2201/4618—Supplying or removing reactants or electrolyte
- C02F2201/46185—Recycling the cathodic or anodic feed
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/10—Energy recovery
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)
- Water Treatment By Electricity Or Magnetism (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a recovery system and a recovery method for waste liquid produced by an ammonium nitrate exchange molecular sieve, which comprises a ceramic membrane filter for pretreating raw water, a resin exchange softening device for removing multivalent ions from pretreated clear liquid, a bipolar membrane electrodialysis device and a hollow fiber degassing membrane device. Send into bipolar membrane system with this waste water in this application and can carry out the material conversion, turn into acid solution and aqueous ammonia solution with containing ammonium inorganic salt solution, then the containing ammonium inorganic salt solution of reconversion removes the absorption ammonium through hollow fiber deammoniation membrane (deammoniation membrane), thereby accomplish and guarantee that the impurity in the solution is not at the intrasystem enrichment, ensure to contain ammonium inorganic salt and continue recycling in production system, and simultaneously, impurity in the solution will follow the discharge in the system along with outer flowing back, realization resource's recycle that so can be better.
Description
Technical Field
The invention relates to the technical field of physical chemistry and electrochemistry, in particular to a system and a method for recovering waste liquid produced by an ammonium nitrate exchange molecular sieve.
Background
The zeolite molecular sieve is an inorganic silicon-containing crystal, and the most important zeolite molecular sieves are generally synthesized by a hydrothermal synthesis method, are sodium type molecular sieves, and have better catalytic activity only by replacing sodium ions in the molecular sieves with hydrogen elements. The exchange treatment of sodium ions is generally carried out using an ammonium ion solution containing 5 to 20% of ammonium-containing inorganic salt, and the remaining ammonium-containing inorganic salt solution is converted into a sodium-containing inorganic salt solution. As the ammonium-containing inorganic salt belongs to nitrogen-containing substances, a large amount of ammonium-containing inorganic salt can pollute the environment, and the difficulty in sewage system treatment is improved.
Electrodialysis refers to the process of passing an electric current through a substance to cause a chemical change. Has been widely used in non-ferrous metal metallurgy, chlor-alkali and inorganic salt production and organic chemistry industry. The principle is that the charged ions in the solution selectively permeate through the anion-cation exchange membrane and the cation-anion exchange membrane under the action of a direct current electric field by utilizing the selective permeability of the ion exchange membrane, and the purposes of separation and concentration are achieved by adopting different assembly forms.
The solution containing ammonium inorganic salt is a common exchange solution, and has better catalytic activity only by replacing sodium ions in the molecular sieve with hydrogen elements.
At present, industrial ammonium salt-containing water is mainly prepared by acid-base neutralization, and three common recovery methods are available, including an air stripping method, an ion exchange resin method and an electrolytic method.
The stripping method mainly utilizes ammonia nitrogen to mainly use ammonium ions (NH) in the wastewater 4 + ) And free ammonia (NH) 3 ) The states exist, with the equilibrium relationship as follows: NH (NH) 3 +H 2 O—NH 4 + +OH - This relationship is influenced by the pH, at which the equilibrium shifts to the left and the proportion of free ammonia increases. At room temperature, most of ammonia nitrogen exists in the state of ammonium ion at a pH of about 7, whereas at a pH of about 11, the content of free ammonia is about 98, and free ammonia is liable to escape from water, and if aeration is applied, the escape of ammonia from water can be promoted. The purity of the ammonia water product produced by the method can meet the use requirement, but the method can only recover ammonia gas to form ammonia water, and has no removal effect on other anions in the wastewater, so that the subsequent water treatment cost can be increased.
The ion exchange method uses ammonium-containing salt water as a raw material to carry out ion exchange in ion exchange resin; produced by ion exchange method, na is easily brought in when the exchange resin is regenerated + Ion, and Na + The ion content has important influence on the performance of the molecular sieve; furthermore, the ion exchange process produces a large amount of wastewater.
Compared with other processes, the invention is simpler, convenient to operate, low in cost, greatly reduces the discharge of waste water, has no pollution, and enables substances in the waste water to be separated and recycled.
Disclosure of Invention
The invention aims to provide a system and a method for recovering waste liquid produced by an ammonium nitrate exchange molecular sieve, which solve the problems of higher process cost, more complex process and lack of wastewater substance recovery and utilization of the conventional ammonium nitrate exchange molecular sieve produced waste liquid treatment process.
In order to solve the technical problem, the invention adopts the following technical scheme:
the invention provides a recovery system and a recovery method of waste liquid produced by an ammonium nitrate exchange molecular sieve, which comprises a ceramic membrane filter for pretreating raw water, a resin exchange softening device for removing multivalent ions from pretreated clear liquid, a bipolar membrane electrodialysis device and a hollow fiber degassing membrane device, wherein the ceramic membrane filter is used for pre-treating the raw water;
in which NH containing various impurities 4 NO 3 The solution is fed into a ceramic membrane filter through a centrifugal pump, and NH is filtered by a ceramic filter element in the ceramic membrane filter 4 NO 3 Pretreating the solution to enable solid particles larger than the filter holes and insoluble silicon to be intercepted by a filter interface and to be discharged through concentrated solution, so that impurities in the raw water are separated and clear liquid is obtained;
the filtered clear liquid is sent into a resin exchange softening device under the residual pressure, multivalent ions in the solution are exchanged by ammonium ions and are fixed on a resin bed, so that the multivalent ions are removed, and the effluent is sent into an intermediate tank for buffering for later use;
transferring the softened liquid in the middle tank into a bipolar membrane electrodialysis raw water tank, wherein three solutions, namely about 6% nitric acid solution, 1.7% ammonia-containing sodium hydroxide solution and about 1% sodium ion-containing ammonium nitrate solution remained in the raw water tank are obtained after the softened liquid is sent into a bipolar membrane electrodialysis device for treatment; wherein, the 1 percent sodium-containing ammonium nitrate solution is concentrated to about 5 percent by an electrodialysis concentration system and then is sent to a bipolar membrane system together with raw water;
respectively transferring the acid liquor and the alkali liquor produced by the bipolar membrane system into a recovery tank and a raw water tank of the deamination membrane system, wherein the alkali liquor is pumped into a heat exchanger from the raw water tank, exchanges heat with cold water in a plate heat exchanger to be cooled, then sequentially passes through a fiber membrane of the deamination membrane module by a tube pass, returns to the raw water tank after a membrane core, and exchanges the heat remained by the alkali liquor to the acid liquor by the fiber membrane on the way of circularly flowing back to the raw water tank;
wherein the nitric acid absorption liquid in the absorption tank sequentially passes through the deamination membrane module in a mode of pipe pass and alkali liquor countercurrent by a pump, and then circularly flows back to the absorption tank; the ammonia content in the alkali liquor is reduced to below 0.1 percent by repeated circulating operation, and the ammonium nitrate content in the recovery box reaches above 6 percent.
Further optimizing, wherein the ceramic membrane filter comprises a balance cylinder, a feed pump, a membrane assembly, a pressure gauge, a diaphragm valve and a tube pass; wherein, the flow of the clear liquid and the concentrated liquid is adjusted by adjusting the diaphragm valve to control the pressure inside and outside the membrane tube.
Further optimizing, the resin exchange softening device comprises a clear liquid storage tank, a water inlet pump, an ion exchange tower, a full-automatic multi-path control valve, a salt box, a resin catcher, a flow meter, a pressure gauge and a pipe pass; wherein the ion exchange tower is internally filled with high-efficiency strong acid type cation resin which is used for removing high-valence calcium ions, magnesium ions, aluminum ions and the like.
Further optimizing, the bipolar membrane electrodialysis device comprises a membrane stack, a rectifier, an electrical cabinet, a water tank, a pump, a valve and an instrument; under the action of DC electric field, the bipolar membrane stack can dissociate water to obtain H on two sides of the membrane + And OH - (ii) a By utilizing the characteristic, the bipolar membrane electrodialysis system which combines the bipolar membrane and other anion-cation exchange membranes can convert the salt in the ammonium nitrate solution into corresponding acid and alkali without introducing new components.
Further optimizing, wherein the hollow fiber degassing membrane device comprises an ammonia water tank, a nitric acid water tank, an ammonia water circulating pump, a nitric acid circulating pump, a heat exchanger, a membrane assembly, a turbine flowmeter, a pressure gauge, a temperature sensor, a liquid level switch and a tube pass; continuously transferring the ammonia water, the mixed solution of sodium hydroxide and the nitric acid solution separated by the bipolar membrane into a hollow fiber membrane tube through an ammonia water circulating pump, a nitric acid circulating pump and a heat exchanger, and controlling the flow ratio of the ammonia water circulating pump to the nitric acid circulating pump to be 2:1 in the membrane module; a certain partial pressure difference is formed between the inside and the outside of the membrane, and gaseous ammonia crosses the membrane wall from the alkali liquor side with higher partial pressure difference to the acid liquor side with lower ammonia partial pressure difference, so that ammonium nitrate with slowly rising concentration is obtained in a nitric acid water tank.
And further optimizing, wherein the softening resin tower of the resin exchange softening device is regenerated every 2 days, and the regeneration adopts the ammonium nitrate solution finally deprived of sodium ions for resin transformation.
And further optimizing, wherein the ammonium-containing material is one or more of ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium carbonate and ammonium phosphate.
Compared with the prior art, the invention has the beneficial technical effects that: send into bipolar membrane system with this waste water in this application and can carry out the material conversion, turn into acid solution and aqueous ammonia solution with containing ammonium inorganic salt solution, then the containing ammonium inorganic salt solution of reconversion removes the absorption ammonium through hollow fiber deammoniation membrane (deammoniation membrane), thereby accomplish and guarantee that the impurity in the solution is not at the intrasystem enrichment, ensure to contain ammonium inorganic salt and continue recycling in production system, and simultaneously, impurity in the solution will follow the discharge in the system along with outer flowing back, realization resource's recycle that so can be better.
Drawings
The invention is further illustrated in the following description with reference to the drawings.
FIG. 1 is a process flow diagram;
FIG. 2 is a flow diagram of a ceramic membrane filtration apparatus;
FIG. 3 is a schematic diagram of a resin exchange softener;
FIG. 4 is a flow diagram of a bipolar membrane electrodialysis device;
FIG. 5 is a flow diagram of a hollow fiber deammoniation membrane apparatus.
Detailed Description
As shown in fig. 1 to 5, the present embodiment discloses a system for recovering ammonium nitrate exchange molecular sieve output waste liquid, which comprises a ceramic membrane filter for pretreating raw water, a resin exchange softening device for removing multivalent ions from pretreated clear liquid, a bipolar membrane electrodialysis device, and a hollow fiber degassing membrane device;
in this embodiment, as shown in fig. 2, the ceramic membrane filter includes a cleaning tank, a supply pump, a membrane module, a pressure gauge, a diaphragm valve, and a tube pass; wherein the flow of the clear liquid and the concentrated liquid is adjusted by adjusting the diaphragm valve to control the pressure inside and outside the membrane tube.
In this embodiment, as shown in fig. 3, the resin exchange softening device includes a clear liquid storage tank, a water inlet pump, an ion exchange tower, a full-automatic multi-way control valve, a salt tank, a resin catcher, a flow meter, a pressure gauge, and a tube pass; wherein, the inner tank of the ion exchange tower is filled with high-efficiency strong acid type cation resin which is used for removing high-valence calcium ions, magnesium ions, aluminum ions and the like; in order to simplify field operation, the ion exchange tower adopts a full-automatic multi-way control valve to realize operations such as 'working', 'backwashing', 'regeneration', 'slow replacement', 'fast washing', 'salt box water replenishing' and the like, and only proper ammonium nitrate is required to be quantitatively added into a salt box; wherein the softening resin tower of the resin exchange softening device is regenerated every 2 days, and the ammonium nitrate solution which is finally removed of sodium ions is adopted for resin transformation.
In this embodiment, as shown in fig. 4, the bipolar membrane electrodialysis device includes a membrane stack, a rectifier, an electrical cabinet, a water tank, a pump, a valve, and a meter; under the action of DC electric field, the bipolar membrane stack can dissociate water to obtain H on two sides of the membrane + And OH-; by utilizing the characteristic, the bipolar membrane electrodialysis system combining the bipolar membrane and other anion-cation exchange membranes can convert the salt in the ammonium nitrate solution into corresponding acid and alkali without introducing new components.
In this embodiment, as shown in fig. 5, the hollow fiber degassing membrane apparatus includes an ammonia water tank, a nitric acid water tank, an ammonia water circulating pump, a nitric acid circulating pump, a heat exchanger, a membrane module, a turbine flowmeter, a pressure gauge, a temperature sensor, a liquid level switch, and a tube pass; continuously transferring the ammonia water, the mixed solution of sodium hydroxide and the nitric acid solution separated by the bipolar membrane into a hollow fiber membrane tube through an ammonia water circulating pump, a nitric acid circulating pump and a heat exchanger, and controlling the flow ratio of the ammonia water circulating pump to the nitric acid circulating pump to be 2:1 in the membrane module; a certain partial pressure difference is formed between the inside and the outside of the membrane, and gaseous ammonia crosses the membrane wall from the alkali liquor side with higher partial pressure difference to the acid liquor side with lower ammonia partial pressure difference, so that ammonium nitrate with slowly rising concentration is obtained in a nitric acid water tank.
Wherein, a large amount of ammonium-containing inorganic salt produced after the exchange of the molecular sieve can be one or more of ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium carbonate and ammonium phosphate; in this embodiment, the organic ammonium salt may be used.
The specific implementation method comprises the following steps:
in which NH containing various impurities 4 NO 3 The solution is sent into a raw water tank for buffering for standby use (NH) 4 NO 3 The main impurities in the solution are sodium ions and silica), then the solution is sent into a ceramic membrane filter (the ceramic membrane is provided with a high-precision tubular ceramic filter element) through a centrifugal pump, and NH is filtered by the ceramic filter element in the ceramic membrane filter 4 NO 3 Pretreating the solution to enable solid particles larger than the filter pores and insoluble silicon to be intercepted by a filter interface and to be discharged through concentrated solution, so that impurities in the raw water are separated and clear solution is obtained;
the filtered clear liquid is sent into a resin exchange softening device under the residual pressure, multivalent ions in the solution are exchanged by ammonium ions and are fixed on a resin bed, so that the removal of the multivalent ions (mainly high-valence calcium ions, magnesium ions and aluminum ions) is completed, and the effluent of the solution is sent into a middle tank for buffering for later use; wherein the resin exchange softener comprises an ion exchange tower, wherein the salt tank is supplemented with ammonium nitrate from a deamination membrane, wherein NH is contained in the ammonium nitrate 4 + Exchange with multivalent ions;
transferring the softened liquid in the middle tank into a bipolar membrane electrodialysis raw water tank, wherein three solutions, namely a nitric acid solution with the concentration of about 6%, a sodium hydroxide solution with the concentration of 1.7% and an ammonium nitrate solution with the concentration of about 1% of sodium remained in the raw water tank are obtained after the softened liquid is sent into a bipolar membrane electrodialysis device for treatment; wherein the 1% sodium nitrate solution containing sodium is concentrated to about 4% by an electrodialysis concentration system, and then is delivered to a bipolar membrane system together with softened raw water;
respectively transferring the acid liquor and the alkali liquor produced by the bipolar membrane system into a recovery tank and a raw water tank of the deamination membrane system, wherein the alkali liquor is pumped into a heat exchanger from the raw water tank, exchanges heat with cold water in a plate heat exchanger to be cooled, then sequentially passes through a fiber membrane of the deamination membrane module by a tube pass, returns to the raw water tank after a membrane core, and exchanges the heat remained by the alkali liquor to the acid liquor by the fiber membrane on the way of circularly flowing back to the raw water tank;
wherein the nitric acid absorption liquid in the absorption tank sequentially passes through the deamination membrane module in a mode of pipe pass and alkali liquor countercurrent by a pump, and then circularly flows back to the absorption tank; the ammonia content in the alkali liquor is reduced to below 0.1 percent by repeated circulating operation, and the ammonium nitrate content in the recovery box reaches above 6 percent.
In the description of the present invention, it is to be understood that the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate orientations or positional relationships based on those shown in the drawings, and are used merely for convenience in describing the present invention, and do not indicate or imply that the device or element so referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The above embodiments are only for describing the preferred mode of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solution of the present invention by those skilled in the art should fall within the protection scope defined by the claims of the present invention without departing from the spirit of the present invention.
Claims (7)
1. The utility model provides a recovery system of ammonium nitrate exchange molecular sieve output waste liquid which characterized in that:
comprises a ceramic membrane filter for pretreating raw water, a resin exchange softening device for removing multivalent ions from pretreated clear liquid, a bipolar membrane electrodialysis device and a hollow fiber degassing membrane device;
in which NH containing various impurities 4 NO 3 The solution is sent into a ceramic membrane filter through a centrifugal pump and passes through a ceramic filter element in the ceramic membrane filter to NH 4 NO 3 Pretreating the solution to enable solid particles larger than the filter holes and insoluble silicon to be intercepted by a filter interface and to be discharged through concentrated solution, so that impurities in the raw water are separated and clear liquid is obtained;
the filtered clear liquid is sent into a resin exchange softening device under the residual pressure, multivalent ions in the solution are exchanged by ammonium ions and are fixed on a resin bed, so that the multivalent ions are removed, and the effluent is sent into an intermediate tank for buffering for later use;
transferring the softened liquid in the middle tank into a bipolar membrane electrodialysis raw water tank, wherein three solutions, namely about 6% nitric acid solution, 1.7% ammonia-containing sodium hydroxide solution and about 1% sodium ion-containing ammonium nitrate solution remained in the raw water tank are obtained after the softened liquid is sent into a bipolar membrane electrodialysis device for treatment; wherein, the 1 percent sodium-containing ammonium nitrate solution is concentrated to about 4 percent by an electrodialysis concentration system and then is delivered to a bipolar membrane system together with softened raw water;
respectively transferring the acid liquor and the alkali liquor produced by the bipolar membrane system into a recovery tank and a raw water tank of the deamination membrane system, wherein the alkali liquor is pumped into a heat exchanger from the raw water tank, exchanges heat with cold water in a plate heat exchanger to be cooled, then sequentially passes through a fiber membrane of the deamination membrane module by a tube pass, returns to the raw water tank after a membrane core, and exchanges the heat remained by the alkali liquor to the acid liquor by the fiber membrane on the way of circularly flowing back to the raw water tank;
wherein the nitric acid absorption liquid in the absorption tank sequentially passes through the deamination membrane module in a mode of pipe pass and alkali liquor countercurrent by a pump, and then circularly flows back to the absorption tank; the ammonia content in the alkali liquor is reduced to below 0.1 percent by repeated circulating operation, and the ammonium nitrate content in the recovery tank reaches above 6 percent.
2. The system of claim 1, wherein the system is characterized by: the ceramic membrane filter comprises a cleaning tank, a feeding pump, a membrane assembly, a pressure gauge, a diaphragm valve and a tube pass; wherein the flow of the clear liquid and the concentrated liquid is adjusted by adjusting the diaphragm valve to control the pressure inside and outside the membrane tube.
3. The system of claim 1 for recovering spent liquor produced by ammonium nitrate exchange molecular sieve, wherein: the resin exchange softening device comprises a clear liquid storage tank, a water inlet pump, an ion exchange tower, a full-automatic multi-way control valve, a salt tank, a resin catcher, a flow meter, a pressure gauge and a pipe pass; wherein the inner tank of the ion exchange tower is filled with high-efficiency strong acid type cation resin which is used for removing high-valence calcium ions, magnesium ions, aluminum ions and the like.
4. The system of claim 1, wherein the system is characterized by: the bipolar membrane electrodialysis device comprises a membrane stack, a rectifier, an electrical cabinet, a water tank, a pump, a valve and an instrument; under the action of DC electric field, the bipolar membrane stack can dissociate water to obtain H on two sides of the membrane + And OH-; by utilizing the characteristic, the bipolar membrane electrodialysis system which combines the bipolar membrane and other anion-cation exchange membranes can convert the salt in the ammonium nitrate solution into corresponding acid and alkali without introducing new components.
5. The system of claim 1 for recovering spent liquor produced by ammonium nitrate exchange molecular sieve, wherein: the hollow fiber degassing membrane device comprises an ammonia water tank, a nitric acid water tank, an ammonia water circulating pump, a nitric acid circulating pump, a heat exchanger, a membrane module, a turbine flowmeter, a pressure gauge, a temperature sensor, a liquid level switch and a tube side; continuously transferring the ammonia water, the mixed solution of sodium hydroxide and the nitric acid solution separated by the bipolar membrane into a hollow fiber membrane tube through an ammonia water circulating pump, a nitric acid circulating pump and a heat exchanger, and controlling the flow ratio of the ammonia water circulating pump to the nitric acid circulating pump to be 2:1 in the membrane module; a certain partial pressure difference is formed between the inside and the outside of the membrane, and gaseous ammonia crosses the membrane wall from the alkali liquor side with higher partial pressure difference to the acid liquor side with lower ammonia partial pressure difference, so that ammonium nitrate with slowly rising concentration is obtained in a nitric acid water tank.
6. The system of claim 1 for recovering spent liquor produced by ammonium nitrate exchange molecular sieve, wherein: wherein the softening resin tower of the resin exchange softening device is regenerated every 2 days, and the ammonium nitrate solution which is finally removed of sodium ions is adopted for resin transformation.
7. The system of claim 1, wherein the system is characterized by: wherein the ammonium-containing material is one or more of ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium carbonate and ammonium phosphate.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380029A (en) * | 2016-11-30 | 2017-02-08 | 中国科学技术大学 | Integrated device of bipolar membrane electrodialysis and hollow fiber membrane contactor and method for wastewater deaminating |
| CN107188358A (en) * | 2017-07-19 | 2017-09-22 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high-concentration ammonium salt waste water |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106380029A (en) * | 2016-11-30 | 2017-02-08 | 中国科学技术大学 | Integrated device of bipolar membrane electrodialysis and hollow fiber membrane contactor and method for wastewater deaminating |
| CN107188358A (en) * | 2017-07-19 | 2017-09-22 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment system, processing method and the application of high-concentration ammonium salt waste water |
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