CN219991243U - System for preparing hydrogen type molecular sieve - Google Patents
System for preparing hydrogen type molecular sieve Download PDFInfo
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- CN219991243U CN219991243U CN202320008447.8U CN202320008447U CN219991243U CN 219991243 U CN219991243 U CN 219991243U CN 202320008447 U CN202320008447 U CN 202320008447U CN 219991243 U CN219991243 U CN 219991243U
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- ion exchange
- storage tank
- outlet
- bipolar
- membrane
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- 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 98
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 97
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 16
- 239000001257 hydrogen Substances 0.000 title abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 16
- 239000012528 membrane Substances 0.000 claims abstract description 184
- 238000005342 ion exchange Methods 0.000 claims abstract description 112
- 239000002253 acid Substances 0.000 claims abstract description 104
- 238000000909 electrodialysis Methods 0.000 claims abstract description 98
- 239000007788 liquid Substances 0.000 claims abstract description 91
- 238000003860 storage Methods 0.000 claims abstract description 76
- 238000000034 method Methods 0.000 claims abstract description 59
- 239000002699 waste material Substances 0.000 claims abstract description 54
- 238000011010 flushing procedure Methods 0.000 claims abstract description 50
- 239000002002 slurry Substances 0.000 claims abstract description 47
- 239000011347 resin Substances 0.000 claims abstract description 45
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 230000008929 regeneration Effects 0.000 claims abstract description 26
- 238000011069 regeneration method Methods 0.000 claims abstract description 26
- 239000012530 fluid Substances 0.000 claims abstract description 15
- 238000010009 beating Methods 0.000 claims abstract description 12
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 238000005341 cation exchange Methods 0.000 claims description 55
- 239000003011 anion exchange membrane Substances 0.000 claims description 40
- 239000003513 alkali Substances 0.000 claims description 31
- 238000005349 anion exchange Methods 0.000 claims description 19
- 150000003839 salts Chemical class 0.000 claims description 19
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 27
- 239000006227 byproduct Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 34
- 239000000243 solution Substances 0.000 description 27
- 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 23
- 239000008367 deionised water Substances 0.000 description 19
- 229910021641 deionized water Inorganic materials 0.000 description 19
- 239000003729 cation exchange resin Substances 0.000 description 17
- 239000011734 sodium Substances 0.000 description 15
- 239000003792 electrolyte Substances 0.000 description 12
- 239000011268 mixed slurry Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 11
- 238000005086 pumping Methods 0.000 description 10
- 239000002585 base Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 239000003999 initiator Substances 0.000 description 9
- 239000003456 ion exchange resin Substances 0.000 description 9
- 229920003303 ion-exchange polymer Polymers 0.000 description 9
- 239000008151 electrolyte solution Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 230000000149 penetrating effect Effects 0.000 description 7
- 239000002351 wastewater Substances 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 229910001948 sodium oxide Inorganic materials 0.000 description 6
- 238000004846 x-ray emission Methods 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000005284 excitation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000005486 organic electrolyte Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The utility model relates to the technical field of molecular sieves, in particular to a system for preparing a hydrogen type molecular sieve, which comprises the following components: the pulping tank, the ion exchange column filled with resin and the bipolar membrane electrodialysis device are sequentially connected, and the slurry storage tank, the waste liquid storage tank and the acid liquid storage tank are sequentially connected; a three-way valve is arranged above the ion exchange column, and a first inlet, a first outlet and a second inlet in the three-way valve are respectively connected with the beating tank, the ion exchange column and the acid liquid storage tank; the bottom of the ion exchange column is provided with a double-port valve, a second outlet and a third outlet in the double-port valve are respectively connected with the slurry storage tank and the waste liquid storage tank, and the bottom and the top of the ion exchange column are respectively provided with a flushing fluid inlet and a flushing fluid outlet, and can be controlled to perform an exchange process, a back flushing process and a regeneration process in the same ion exchange column. The system carries out electrodialysis on the waste liquid generated in the regeneration process, realizes zero discharge of the waste liquid and also produces sodium hydroxide solution as a byproduct.
Description
Technical Field
The utility model relates to the technical field of molecular sieves, in particular to a system for preparing a hydrogen type molecular sieve.
Background
Molecular sieves are widely used in petrochemical processes as solid acid catalysts. The most important molecular sieves for industrial use are Y, ZSM-5 and Beta, etc. The molecular sieve raw powder is usually in a sodium form, and can be used as an active component of an acid catalyst only after being prepared into a hydrogen form. Taking the production process of the Y-type molecular sieve as an example, the molecular sieve raw powder NaY is firstly subjected to ammonium exchange to prepare the ammonium molecular sieve NH 4 Y is then calcined to convert it into hydrogen form of molecular sieve HY. Wherein the ammonium exchange process comprises mixing molecular sieve with ammonium salt (such as ammonium sulfate) solution, and Na in molecular sieve + With NH in solution 4 + Exchange reaction occurs to produce the ammonium molecular sieve. NH due to chemical equilibrium and molecular sieve structure limitations 4 + It is impossible to completely replace Na at a time + To obtain Na 2 The molecular sieve with low O content needs to be repeated for a plurality of times in the ammonium exchange process, and a large amount of waste water with exceeding ammonium nitrogen standard is generated. At present, every 1t of finished Y-shaped molecular sieve produced by a catalyst factory approximately produces 20t of NH 4 + Waste water with the mass concentration of about 5000-6000 mg/L. In order to meet the emission standard (GB 8978-1996) less than 15mg/L, the waste water is required to be treated, and the energy consumption and the cost are high. Thus in order to meet the increasingly stringentEnvironmental regulations and plant requirements for economic benefits are stringent to develop clean, low cost molecular sieve Na removal + Techniques.
The prior art relates to an ion exchange process of direct contact or indirect contact of ion exchange resin and molecular sieve, and the ion exchange method has the outstanding advantages of good water quality, lower production cost, mature technology and the like when used for desalting, but the treatment method of the resin which is invalid after the exchange is regenerated by using an aqueous solution of inorganic acid or organic acid, and a large amount of washing wastewater containing salt and acid is produced in the process, so that the method is uneconomical and not environment-friendly.
Disclosure of Invention
The utility model aims to solve the problems that the existing system for preparing the hydrogen type molecular sieve needs to periodically regenerate resin by acid and alkali due to the failure of ion exchange resin, generates a large amount of salt-containing and acid-containing wastewater to be treated, and the like, and provides a novel system for preparing the hydrogen type molecular sieve, which realizes high-efficiency ion exchange of the molecular sieve and has no waste gas and no wastewater discharge; meanwhile, the system combines the regeneration process of the ion exchange column with the bipolar membrane electrodialysis device, so that the recycling of the regeneration liquid is realized, and the byproduct sodium hydroxide is produced.
In order to achieve the above object, the present utility model provides a system for preparing a molecular sieve in hydrogen form, the system comprising: the pulping tank, the ion exchange column filled with resin and the bipolar membrane electrodialysis device are sequentially connected, and the slurry storage tank, the waste liquid storage tank and the acid liquid storage tank are sequentially connected;
A three-way valve is arranged above the ion exchange column, and a first inlet, a first outlet and a second inlet in the three-way valve are respectively connected with the beating tank, the ion exchange column and the acid liquid storage tank; the bottom of the ion exchange column is provided with a double-port valve, a second outlet and a third outlet in the double-port valve are respectively connected with the slurry storage tank and the waste liquid storage tank, and the bottom and the top of the ion exchange column are respectively provided with a flushing fluid inlet and a flushing fluid outlet, and can be controlled to perform an exchange process, a back flushing process and a regeneration process in the same ion exchange column.
Preferably, the beating tank is used for mixing and heating the Na-type molecular sieve, the ion exchange initiator and the water to obtain mixed slurry; the ion exchange column is used for exchanging the mixed slurry with resin to obtain hydrogen-containing molecular sieve slurry and failure resin converted from resin; or, the method is used for back flushing the failure resin and the water to obtain back flushed resin and flushing fluid; or regenerating the back-washed resin and the acid liquor to obtain regenerated resin and waste liquor; the bipolar membrane electrodialysis device is used for electrodialysis the waste liquid to obtain acid liquor and alkali liquor; the slurry storage tank is used for storing the hydrogen-containing molecular sieve slurry; the waste liquid storage tank is arranged at the bottom of the ion exchange column and on a connecting pipeline of the bipolar membrane electrodialysis device and is used for storing the waste liquid; the acid liquor storage tank is arranged on a second inlet of the three-way valve and a connecting pipeline of the bipolar membrane electrodialysis device and is used for storing the acid liquor.
Preferably, the first inlet, the second inlet, the first outlet, the second outlet, the third outlet, the rinse inlet and the rinse outlet each independently have an operating state and a closed state.
Preferably, when the first inlet, the first outlet and the second outlet are in a working state, the second inlet, the third outlet, the flushing liquid inlet and the flushing liquid outlet are in a closed state, and the ion exchange column performs the exchange process; wherein in the exchange process, na in the hydrogen-containing molecular sieve slurry discharged from the second outlet 2 The O content is less than or equal to 3wt%; otherwise, the ion exchange column performs the back flushing process.
Preferably, when the flushing liquid inlet and the flushing liquid outlet are in a working state, the ion exchange column performs the back flushing process when the first inlet, the second inlet, the first outlet, the second outlet and the third outlet are in a closed state; wherein, in the back flushing process, the flushing liquid discharged from the back flushing outlet contains molecular sieve particles; otherwise, the ion exchange column performs the regeneration process.
Preferably, when the second inlet, the first outlet and the third outlet are in a working state, the ion exchange column performs the regeneration process when the first inlet, the second outlet, the flushing fluid inlet and the flushing fluid outlet are in a closed state; wherein, in the regeneration process, the pH value of the waste liquid discharged from the third outlet is more than or equal to 3; otherwise, the ion exchange column performs the exchange process.
Preferably, the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with counter electrodes, at least two bipolar membranes and at least one cation exchange membrane which are arranged between the counter electrodes, and the bipolar membranes and the cation exchange membranes are alternately arranged; wherein an acid chamber is formed between the cation exchange layer and the cation exchange membrane in the bipolar membrane and is used for carrying out electrodialysis on the waste liquid; an alkali chamber is formed between the anion exchange layer and the cation exchange membrane in the bipolar membrane and is used for receiving Na ions penetrating through the cation exchange membrane; an electrode chamber formed between the counter electrode and the bipolar membrane is used for conducting electric charges electrolytically from the aqueous electrolyte solution when a direct current is applied to the counter electrode.
Preferably, the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with a counter electrode, at least two bipolar membranes and at least one anion exchange membrane which are arranged between the counter electrodes, and the bipolar membranes and the anion exchange membranes are alternately arranged; wherein an acid chamber is formed between the cation exchange layer and the anion exchange membrane in the bipolar membrane and is used for receiving sulfate ions penetrating through the anion exchange membrane; an alkali chamber is formed between the anion exchange layer and the anion exchange membrane in the bipolar membrane and is used for carrying out electrodialysis on the waste liquid; an electrode chamber formed between the counter electrode and the bipolar membrane is used for conducting electric charges electrolytically from the aqueous electrolyte solution when a direct current is applied to the counter electrode.
Preferably, the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with counter electrodes, at least two bipolar membranes, at least one group of cation exchange membranes and anion exchange membranes, which are adjacently arranged, are arranged between the counter electrodes, and the cation exchange membranes and the anion exchange membranes are alternately arranged with the bipolar membranes; wherein a salt chamber is formed between the cation exchange membrane and the anion exchange membrane and is used for carrying out electrodialysis on the waste liquid; an acid chamber is formed between the cation exchange layer and the anion exchange membrane in the bipolar membrane, and an alkali chamber is formed between the anion exchange layer and the cation exchange membrane in the bipolar membrane, and the acid chamber and the alkali chamber are respectively and independently used for receiving sulfate ions penetrating through the anion exchange membrane and Na ions penetrating through the cation exchange membrane; the electrode chamber formed by the counter electrode and the bipolar membrane is used for conducting electric charges electrolytically by the electrolyte aqueous solution when direct current is applied to the counter electrode.
Preferably, the flushing liquid outlet is connected to the beating tank for returning the flushing liquid and mixing it into the mixed slurry.
Through the technical scheme, the system comprising the beating tank, the ion exchange column, the bipolar membrane electrodialysis device, the slurry storage tank, the waste liquid storage tank, the acid liquid storage tank, the three-way valve and the double-port valve is adopted, and the three processes of exchange, back flushing and regeneration of the ion exchange column are realized by regulating and controlling the states of the three-way valve and the double-port valve; combining a bipolar membrane electrodialysis device to prepare acid liquor by using waste liquid generated in the resin regeneration process as a raw material of electrodialysis, and applying the acid liquor to regeneration of the failure resin; the system also returns and mixes the rinse solution into the beater tank. Therefore, the system carries out electrodialysis on the waste liquid generated in the regeneration process, realizes zero discharge of the waste liquid and also produces sodium hydroxide solution as a byproduct.
Drawings
FIG. 1 is a system for preparing a molecular sieve in hydrogen form provided by the present utility model;
FIG. 2 is a schematic illustration of a first arrangement of membrane stacks and counter electrodes of a bipolar membrane electrodialysis device according to the utility model;
FIG. 3 is a schematic illustration of a second arrangement of membrane stacks and counter electrodes of a bipolar membrane electrodialysis device according to the utility model;
fig. 4 is a schematic diagram of a third arrangement of membrane stacks and counter electrodes of a bipolar membrane electrodialysis device according to the utility model.
Description of the reference numerals
I. Beating tank II, ion exchange column III and bipolar membrane electrodialysis device
IV, slurry storage tank V, three-way valve VI, double-port valve VII and waste liquid storage tank
VIII, acid liquor storage tank s1, first inlet s2, second inlet p1, first outlet
p2, second outlet p3, third outlet q1, rinse inlet q2, rinse outlet
11. Mixed slurry 12, resin 13, hydrogen-containing molecular sieve slurry
14. Flushing liquor 15, acid liquor 16, waste liquor 17 and alkali liquor
1. Anion exchange layer 2, cation exchange layer 3, cation exchange membrane 4, positive electrode
5. Negative electrode 6, anion exchange membrane 7, aqueous electrolyte solution 8, water
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the present utility model, unless specifically stated otherwise, the terms "first," "second," and "third" do not denote a sequential order, nor are they intended to be limiting of various materials or steps, but are merely used to distinguish one from another. For example, "first", "second" and "third" of "first outlet", "second outlet" and "third outlet" are used only to indicate that this is not the same outlet.
In the present utility model, unless specified otherwise, the "top" of the container refers to the position of the container from top to bottom by 0-10%; the "upper portion" of the container refers to the 10-40% position of the container from top to bottom; "middle" of the container refers to the 40-60% position of the container from top to bottom; the "lower portion" of the container refers to the 60-90% position of the container from top to bottom; the "bottom" of the container refers to the 90-100% position of the container from top to bottom.
The present utility model provides a system for preparing a molecular sieve in hydrogen form, as shown in fig. 1, comprising: the pulping tank I, the ion exchange column II filled with resin 12 and the bipolar membrane electrodialysis device III are sequentially connected, and the slurry storage tank IV, the waste liquid storage tank VII and the acid liquid storage tank VIII are connected;
A three-way valve V is arranged above the ion exchange column II, and a first inlet s1, a first outlet p1 and a second inlet s2 in the three-way valve V are respectively connected with the beating tank I, the ion exchange column II and the acid liquid storage tank VIII; the bottom of the ion exchange column II is provided with a double-port valve VI, a second outlet p2 and a third outlet p3 in the double-port valve VI are respectively connected with the slurry storage tank IV and the waste liquid storage tank VII, and the bottom and the top of the ion exchange column II are respectively provided with a flushing fluid inlet q1 and a flushing fluid outlet q2, and can be controlled to perform an exchange process, a back flushing process and a regeneration process in the same ion exchange column.
In the utility model, without special description, a double-port valve VI is arranged at the bottom of the ion exchange column II, and the second outlet p2 and the third outlet p3 of the double-port valve VI are respectively connected with the slurry storage tank IV and the waste liquid storage tank VII, which means that the second outlet p2 of the double-port valve VI is connected with the bottom of the ion exchange column II and the slurry storage tank IV, and the third outlet p3 is connected with the bottom of the ion exchange column II and the waste liquid storage tank VII.
In the utility model, the exchange process, the back flushing process and the regeneration process in the ion exchange column cannot exist at the same time under the condition of no special condition, and only one of the exchange process, the back flushing process and the regeneration process exists.
In the present utility model, preferably, as shown in fig. 1, the beating tank I is used for mixing Na-type molecular sieve, ion exchange initiator and water and then heating to obtain mixed slurry 11; the ion exchange column II is used for exchanging the mixed slurry 11 and the resin 12 to obtain hydrogen-containing molecular sieve slurry 13 and a spent resin converted from the resin 12; or, the method is used for back flushing the failure resin and water to obtain back-flushed resin and flushing fluid 14; or, the resin and the acid liquor 15 after back flushing are regenerated to obtain regenerated resin and waste liquor 16; the bipolar membrane electrodialysis device III is used for electrodialysis the waste liquid 16 to obtain acid liquor 15 and alkali liquor 17; the slurry storage tank IV is used for storing the hydrogen-containing molecular sieve slurry 13; the waste liquid storage tank VII is arranged at the bottom of the ion exchange column II and on a connecting pipeline of the bipolar membrane electrodialysis device III and is used for storing the waste liquid 16; the acid liquor storage tank VIII is arranged on a connecting pipeline of the second inlet s2 in the three-way valve V and the bipolar membrane electrodialysis device III and is used for storing the acid liquor 15.
In the present utility model, the mass ratio of the Na-type molecular sieve to water can be adjusted within a wide range, so long as at least part of the alkali metal ions are allowed to be exchanged by H in the cation exchange resin + Or other cation substitution. Preferably, the mass ratio of the Na-type molecular sieve to the water is 1:5-20, more preferably 1:5-10.
In the present utility model, preferably, the weight ratio of Na-type molecular sieve to ion exchange initiator on a dry basis is 100:0.001-1; the heating temperature is 20-80 ℃.
In the present utility model, preferably, the flow rate of the mixed slurry during the exchange is 3 to 30mL/min; in the regeneration process, the flow rate of the acid liquor is 3-20mL/min.
In the present utility model, preferably, the electrodialysis has a current density of 1 to 10000A/m 2 Preferably 100-5000A/m 2 Most preferably 500-1000A/m 2 The method comprises the steps of carrying out a first treatment on the surface of the The temperature is 0-100deg.C, preferably 20-60deg.C. Wherein the current density parameter is the ratio of the current applied to the counter electrode in the bipolar membrane electrodialysis device to the cross-sectional area of the membrane stack in the bipolar membrane electrodialysis device.
In the present utility model, preferably, the conditions for the regeneration include: the temperature is 0-40deg.C, preferably 20-40deg.C; the time may be 0.1 to 5 hours, preferably 0.5 to 2 hours. The concentration of the acid solution is 0.5-2mol/L, preferably 0.5-1mol/L.
In the present utility model, exchangeable release in the failure resin The cation is metal cation, and during the regeneration process, the cation and H in the acid liquor + Performing ion exchange to obtain regenerated resin, namely hydrogen-type resin; and anions in the acid liquor can enter the waste liquor because the anions do not participate in regeneration. Thus, the waste liquid can be recycled as a feed liquid for the bipolar membrane electrodialysis step without additional addition of electrolyte. Of course, it will be appreciated by those skilled in the art that when it is desired to further increase the concentration of the acid liquor or the anions in the waste liquor are deficient, electrolyte may be added in addition to the waste liquor to increase the concentration of the anions. The electrolyte may be used in such an amount that the concentration of anions in the liquid phase satisfies 0.01 to 10mol/L, preferably 0.5 to 8mol/L, more preferably 1 to 5mol/L.
The spent resin is regenerated according to the utility model, and the bipolar membrane electrodialysis step and the ion exchange step can be cycled multiple times. The number of the above-mentioned cycles is not particularly limited, and generally the number of the above-mentioned cycles may be such that 98% or more of the hydrogen-based resin is finally obtained.
In the present utility model, the resin is selected from cation exchange resins, and may be, for example, a strong acid type cation exchange resin or a weak acid type cation exchange resin. The ion exchange group of the cation exchange resin may be appropriately selected depending on the specific conditions of use, and is not particularly limited. In particular, the ion exchange groups of the strong acid cation exchange resin are preferably-SO 3 H groups, the ion exchange groups of the weak acid cation exchange resin are preferably-COOH groups.
In the present utility model, the volume exchange capacity of the cation exchange resin means the number of moles of ion exchange groups per unit volume of the ion exchange resin measured under the conditions specified in GB/T8144-2008.
The present utility model is not particularly limited in the working exchange capacity of the cation exchange resin. For example, the cation exchange resin may be a strong acid, and its working exchange capacity may be 0.5 to 3mmol/mL, more preferably 1.5 to 3mmol/mL. Ion exchange resins having a working exchange capacity within the above range are commercially available, for example: type 001×7, type 001×14.5, type D72 commercially available from the university of south open chemical plant; the cation exchange resin can also be in a weak acid form, and the exchange capacity can be 1-5mmol/mL. Ion exchange resins having a working exchange capacity within the above range are commercially available, for example: a commercially available D113 resin had an exchange capacity of 4.2mol/mL.
In the present utility model, the sphericity of the cation exchange resin is not particularly limited. The sphere ratio of the cation exchange resin is preferably 95% or more from the viewpoint of further improving the mechanical strength of the resin. In the present utility model, the cation exchange resin has a uniformity coefficient of 1.05 to 1.6, preferably 1.05 to 1.4. The sphericity parameter refers to the percentage of the number of spherical particles of the resin in total particles; the uniformity coefficient parameter refers to the ratio of the diameter of the mesh that can pass 60% by volume of the resin to the diameter of the mesh that can pass 10% by volume of the resin.
In the present utility model, the conditions under which the molecular sieve slurry is contacted with the resin are not particularly limited, and preferably, the temperature of the mixed contact is 20 to 80 ℃, preferably 50 to 80 ℃, in order to facilitate sufficient ion exchange; the time is 5-360min, preferably 5-120min.
According to the above embodiments, the method and conditions for drying the molecular sieve are well known to those skilled in the art, for example, one or more of natural drying, vacuum drying, and forced air drying; the drying temperature is usually 50-120deg.C, and the drying time can be 1-20 hr.
In the present utility model, preferably, the first inlet, the second inlet, the first outlet, the second outlet, the third outlet, the rinse liquid inlet, and the rinse liquid outlet each independently have an operating state and a closed state. In the present utility model, the operating state refers to the open state unless otherwise specified.
In the present utility model, preferably, as shown in fig. 1, the ion exchange column II performs the exchange process while the first inlet s1, the first outlet p1, and the second outlet p2 are in an operating state, and while the second inlet s2, the third outlet p3, the rinse inlet q1, and the rinse outlet q2 are in a closed state.
In the present utility model, preferably, as shown in FIG. 1, na in the hydrogen-containing molecular sieve slurry 13 discharged from the second outlet during the exchange 2 The O content is less than or equal to 3wt%; otherwise, the ion exchange column performs the back flushing process.
In the present utility model, preferably, as shown in fig. 1, when the rinse liquid inlet q1 and the rinse liquid outlet q2 are in an operating state, the ion exchange column II performs the back washing process while the first inlet s1, the second inlet s2, the first outlet p1, the second outlet p2, and the third outlet p3 are in a closed state.
In the present utility model, preferably, as shown in fig. 1, during the back flushing, the flushing liquid 14 discharged from the back flushing outlet contains molecular sieve particles; otherwise, the ion exchange column II performs the regeneration process.
In the present utility model, preferably, as shown in fig. 1, the ion exchange column II performs the regeneration process when the first inlet s1, the second outlet p2, the rinse liquid inlet q1, and the rinse liquid outlet q2 are in a closed state while the second inlet s2, the first outlet p1, and the third outlet p3 are in an operating state.
In the present utility model, preferably, as shown in FIG. 1, the pH of the waste liquid 16 discharged from the third outlet is not less than 3 during the regeneration process; otherwise, the ion exchange column II performs the exchange process.
The schematic diagram of the first arrangement mode of the membrane stack and the counter electrode of the bipolar membrane electrodialysis device provided by the utility model is shown in fig. 2, and as can be seen from fig. 2, the bipolar membrane electrodialysis device III includes: a polar frame in which counter electrodes (i.e., positive electrode 4 and negative electrode 5) are disposed, and at least two bipolar membranes and at least one cation exchange membrane 3 disposed between the counter electrodes, with the bipolar membranes and cation exchange membranes 3 being alternately disposed;
wherein an acid chamber is formed between the cation exchange layer 2 and the cation exchange membrane 3 in the bipolar membrane for subjecting the waste liquid 16 to the electrodialysis; an alkali chamber is formed between the anion exchange layer 1 and the cation exchange membrane 3 in the bipolar membrane and is used for receiving Na ions penetrating through the cation exchange membrane; an electrode chamber formed between the counter electrode and the bipolar membrane (i.e., an electrode chamber formed between the positive electrode 4 and the anion exchange layer 1, an electrode chamber formed between the negative electrode 5 and the cation exchange layer 2) is used to electrolytically conduct electric charges to the aqueous electrolyte solution 7 when a direct current is applied to the counter electrode.
In the bipolar membrane electrodialysis device shown in fig. 2, water 8 enters an acid chamber between a cation exchange layer 2 and an anion exchange membrane 6 in a bipolar membrane, waste liquid 16 enters an alkali chamber between an anion exchange layer l and an anion exchange membrane 6 in the bipolar membrane, an electrode chamber between a positive electrode 4 and an anion exchange layer 1 in the bipolar membrane and an electrode chamber between a negative electrode 5 and the cation exchange layer 2 in the bipolar membrane are filled with an electrolyte aqueous solution 7, and direct current is applied to the positive electrode 4 and the negative electrode 5; thereby generating acid liquor 15 in the acid chamber and alkali liquor 17 in the alkali chamber.
In the present utility model, the bipolar membrane electrodialysis device shown in fig. 2 has only one acid compartment and one base compartment, but it will be understood by those skilled in the art that the bipolar membrane electrodialysis device may have a plurality of acid compartments and a plurality of base compartments, as long as the number of bipolar membranes and cation exchange membranes is increased accordingly, and the bipolar membranes and cation exchange membranes are alternately arranged between the counter electrodes in the manner shown in fig. 2. The plurality of acid chambers may be in a parallel relationship or a series relationship, and the plurality of base chambers may be in a parallel relationship.
The schematic diagram of the second arrangement mode of the membrane stack and the counter electrode of the bipolar membrane electrodialysis device provided by the utility model is shown in fig. 3, and as can be seen from fig. 3, the bipolar membrane electrodialysis device III includes: a polar frame in which counter electrodes (i.e., positive electrode 4 and negative electrode 5) are disposed, and at least two bipolar membranes and at least one anion exchange membrane 6 disposed between the counter electrodes, the bipolar membranes and the anion exchange membranes being alternately disposed;
wherein an acid chamber is formed between the cation exchange layer 2 and the anion exchange membrane 6 in the bipolar membrane and is used for receiving sulfate ions passing through the anion exchange membrane 6; an alkali chamber is formed between the anion exchange layer 1 and the anion exchange membrane 6 in the bipolar membrane and is used for carrying out electrodialysis on the waste liquid 16; an electrode chamber formed between the counter electrode and the bipolar membrane (i.e., an electrode chamber formed between the positive electrode 4 and the anion exchange layer 1, an electrode chamber formed between the negative electrode 5 and the cation exchange layer 2) is used to electrolytically conduct electric charges to the aqueous electrolyte solution 7 when a direct current is applied to the counter electrode.
In the bipolar membrane electrodialysis device shown in fig. 3, water 8 enters an acid chamber between a cation exchange layer 2 and an anion exchange membrane 6 in a bipolar membrane, waste liquid 16 enters an alkali chamber between an anion exchange layer l and an anion exchange membrane 6 in the bipolar membrane, an electrode chamber between a positive electrode 4 and an anion exchange layer 1 in the bipolar membrane and an electrode chamber between a negative electrode 5 and the cation exchange layer 2 in the bipolar membrane are filled with an aqueous electrolyte solution 7, direct current is applied to the positive electrode 4 and the negative electrode 5, thereby acid liquid 15 is generated in the acid chamber, and alkali liquid 16 is generated in the alkali chamber.
In the present utility model, the bipolar membrane electrodialysis device shown in fig. 3 has only one acid compartment and one base compartment, but it will be understood by those skilled in the art that the bipolar membrane electrodialysis device may have a plurality of acid compartments and a plurality of base compartments, as long as the number of bipolar membranes and anion exchange membranes is increased accordingly, and the bipolar membranes and anion exchange membranes are alternately arranged between the counter electrodes in the manner shown in fig. 3. The plurality of acid chambers may be in a parallel relationship or a series relationship, and the plurality of base chambers may be in a parallel relationship.
The schematic diagram of the third arrangement mode of the membrane stack and the counter electrode of the bipolar membrane electrodialysis device provided by the utility model is shown in fig. 4, and as can be seen from fig. 4, the bipolar membrane electrodialysis device III includes: a polar frame in which counter electrodes (i.e., positive electrode 4 and negative electrode 5) are disposed, and at least two bipolar membranes, at least one group of cation exchange membranes 3 and anion exchange membranes 6 disposed adjacently, disposed between the counter electrodes, and the cation exchange membranes 3 and anion exchange membranes 6 are disposed alternately with the bipolar membranes;
Wherein a salt chamber is formed between the cation exchange membrane 3 and the anion exchange membrane 6 for subjecting the waste liquid 16 to the electrodialysis; an acid chamber is formed between the cation exchange layer 2 and the anion exchange membrane 6 in the bipolar membrane, and an alkali chamber is formed between the anion exchange layer 1 and the cation exchange membrane 3 in the bipolar membrane, and the acid chamber and the alkali chamber are respectively used for receiving sulfate ions penetrating through the anion exchange membrane and Na ions penetrating through the cation exchange membrane independently; the electrode chamber formed by the counter electrode and the bipolar membrane (i.e., the electrode chamber formed between the positive electrode 4 and the anion exchange layer 1, the electrode chamber formed between the negative electrode 5 and the cation exchange layer 2) serves to electrolytically conduct electric charges to the aqueous electrolyte solution 7 when a direct current is applied to the counter electrode.
In the bipolar membrane electrodialysis device shown in fig. 4, the waste liquid 16 enters a salt chamber between the cation exchange membrane 3 and the anion exchange membrane 6, water 8 enters an acid chamber between the cation exchange layer 2 and the anion exchange membrane 6 in the bipolar membrane and an alkali chamber between the anion exchange layer l and the cation exchange membrane 3 in the bipolar membrane, an electrode chamber between the positive electrode 4 and the anion exchange layer l in the bipolar membrane and an electrode chamber between the negative electrode 5 and the cation exchange layer 2 in the bipolar membrane are filled with an electrolyte aqueous solution 7, and an electric current is applied to the positive electrode 4 and the negative electrode 5, thereby generating an acid solution 15 in the acid chamber and an alkali solution 17 in the alkali chamber.
In the present utility model, the bipolar membrane electrodialysis device shown in fig. 4 has only one acid compartment, one base compartment and one salt compartment, but it will be understood by those skilled in the art that the bipolar membrane electrodialysis device may have a plurality of acid compartments, a plurality of base compartments and a plurality of salt compartments, as long as the numbers of bipolar membranes, cation exchange membranes and anion exchange membranes are increased accordingly, and the bipolar membranes, cation exchange membranes and anion exchange membranes are alternately arranged between the counter electrodes in the manner shown in fig. 4. The plurality of salt compartments may be in a parallel relationship or a series relationship, and the plurality of acid compartments and the plurality of base compartments may be in a parallel relationship.
In the present utility model, there is a wide range of choices for the ratio of electrolyte to water in the aqueous electrolyte solution filled in the electrode chamber. Preferably, the weight ratio of the electrolyte to the water in the electrolyte aqueous solution is 1:10-400, preferably 1:50-100; wherein the electrolyte is selected from inorganic electrolyte and/or organic electrolyte, and the inorganic electrolyte is selected from at least one of sodium sulfate, sodium nitrate, sodium phosphate, sodium hydrogen phosphate, sodium dihydrogen phosphate, potassium nitrate, potassium phosphate, potassium hydrogen phosphate, potassium dihydrogen phosphate, sodium oxide and potassium oxide; the organic electrolyte is selected from at least one of formic acid, acetic acid, sodium formate and potassium formate.
Although the present utility model only provides the above three arrangements of the membrane stack and the counter electrode, the arrangement of the membrane stack and the counter electrode suitable for use in the bipolar membrane electrodialysis device of the present utility model is not limited thereto, as long as the arrangement of the membrane stack and the counter electrode in the bipolar membrane electrodialysis device can cause the bipolar membrane electrodialysis device to electrodialysis the waste liquid to obtain an acid solution.
In the present utility model, preferably, as shown in fig. 1, the washing liquid outlet q2 is connected to the beating tank I for returning and mixing the washing liquid 14 into the mixed slurry 11.
The present utility model will be described in detail by examples.
X-ray fluorescence spectrometry the composition of the sample was measured using a Japanese national science D/MAX-IIIA X-ray fluorescence spectrometer (using a rhodium target, excitation power supply 50kV, excitation current 50 mA).
The model of the bipolar membrane electrodialysis device is as follows: an ACILYZER-02 type electrodialysis device, wherein the membrane stack size is 100×400mm; bipolar membranes are commercially available from japan asiatology company under the model BP-1; cation exchange membranes were commercially available from Shanghai chemical plant under the model 3362-BW; the anion exchange membranes were commercially available from Shanghai chemical plant under the model 3361-BW. The ion exchange column is a glass column with the height of 40cm and the diameter of 1.5cm, and the outer layer of the ion exchange column is wrapped by a heat insulation material.
The styrene strong acid cation exchange resin with the trade mark of 001 multiplied by 7 is gel type, the particle diameter is 0.5-0.8mm, and the mass total exchange capacity is 1.8mmol/mL.
The styrene strong acid cation exchange resin with the trade mark of 001 multiplied by 14.5 is gel type, the particle diameter is 0.5-1mm, and the mass total exchange capacity is 1.8mmol/mL.
The acrylic weak acid cation exchange resin with the brand D113 is macroporous, the particle diameter is 0.5-1mm, and the mass total exchange capacity is 4.2mmol/mL.
The molecular sieve is the product of the crystallization of the long-term catalyst factory, and the NaY molecular sieve Na 2 The O content was 11wt%, the crystallinity was 84.1% and the unit cell constant was 24.66; na in ZSM-5 molecular sieve 2 The O content is 5wt%, the crystallinity is 95%, and the silicon-aluminum ratio is 60; na in NaX molecular sieves 2 The O content was 4.2wt%, the crystallinity was 95% and the unit cell constant was 24.95.
Examples 1-5 were carried out in a system for preparing a molecular sieve in hydrogen form as shown in figure 1, comprising: the pulping tank I, the ion exchange column II filled with resin 12 and the bipolar membrane electrodialysis device III are sequentially connected, and the slurry storage tank IV, the waste liquid storage tank VII and the acid liquid storage tank VIII are connected;
a three-way valve V is arranged above the ion exchange column II, and a first inlet s1, a first outlet p1 and a second inlet s2 in the three-way valve V are respectively connected with the beating tank I, the ion exchange column II and the acid liquid storage tank VIII; the bottom of the ion exchange column II is provided with a double-port valve VI, a second outlet p2 and a third outlet p3 in the double-port valve VI are respectively connected with a slurry storage tank IV and a waste liquid storage tank VII, and the bottom and the top of the ion exchange column II are respectively provided with a flushing fluid inlet q1 and a flushing fluid outlet q2, and can be controlled to perform an exchange process, a back flushing process and a regeneration process in the same ion exchange column;
The pulping tank I is used for mixing the Na-type molecular sieve, the ion exchange initiator and water and then heating to obtain mixed slurry 11; the ion exchange column II is used for exchanging the mixed slurry 11 and the resin 12 to obtain hydrogen-containing molecular sieve slurry 13 and a spent resin converted from the resin 12; or, the method is used for back flushing the ineffective resin and water to obtain back-flushed resin and flushing fluid 14; or, the method is used for regenerating the resin and the acid liquor 15 after back flushing to obtain regenerated resin and waste liquor 16; the bipolar membrane electrodialysis device III is used for electrodialysis the waste liquid 16 to obtain acid liquor 15 and alkali liquor 17; the slurry storage tank IV is used for storing hydrogen-containing molecular sieve slurry 13; the waste liquid storage tank VII is arranged at the bottom of the ion exchange column II and on a connecting pipeline of the bipolar membrane electrodialysis device III and is used for storing waste liquid 16; the acid liquor storage tank VIII is arranged on a connecting pipeline between the second inlet s2 in the three-way valve V and the bipolar membrane electrodialysis device III and is used for storing acid liquor 15; a flushing liquid outlet q2 is connected to the beating tank I for returning and mixing the flushing liquid 14 into the mixed slurry 11.
Example 1
1) And (3) reversely washing an ion exchange column which is failed to exchange with the NaY molecular sieve by deionized water until effluent liquid is clear and free of molecular sieve particles. The ion exchange column was packed with 55mL (dry mass 32 g) of a 001X 7 brand ion exchange resin.
2) Pumping the acid liquor obtained by electrodialysis into the ineffective ion exchange column from top to bottom by an acid liquor storage tank, detecting the pH value of effluent liquid in the ion exchange column, stopping acid liquor feeding when the pH value is less than 3, and flushing with deionized water until the pH value is more than 4. The concentration of the acid liquor in the storage tank is 0.9mol/L.
3) Introducing the salt-containing solution flowing out of the lower end of the ion exchange column in 2) into a waste liquid storage tank. To the salt-containing solution was added 4g of Na 2 SO 4 And filling the liquid phase into an acid chamber storage tank of the bipolar membrane electrodialysis device, simultaneously adding 1000g of deionized water into an alkali chamber storage tank of the bipolar membrane electrodialysis device, and adding 1000g of 0.25mol/L NaOH solution into an electrode chamber storage tank. Switching on a circulating pump power supply of the bipolar membrane electrodialysis device, starting the circulating pump, starting a direct current power supply between opposite electrodes of the bipolar membrane electrodialysis device after circulation is normal, and regulating voltage to enable current density to be 500A/m 2 Electrodialysis was carried out at 30 ℃.
4) 1000mL of deionized water was added to the beaker, and 100g of NaY molecular sieve (dry basis) was added thereto, and mechanically stirred to obtain a molecular sieve slurry. 1.1g Na was added 2 SO 4 As an exchange initiator, preheating to an exchange temperature of 70 ℃;
5) Pumping the obtained molecular sieve slurry into a regenerated ion exchange column of 2) from top to bottom, wherein the flow speed is 5mL/min, receiving the flowing molecular sieve slurry below the ion exchange column, sampling 40mL at intervals of 20min, and taking 10 times;
6) And respectively carrying out suction filtration on the molecular sieve slurry samples taken each time, and respectively drying filter cakes at 120 ℃ to obtain 10 parts of Y-type molecular sieve.
The sodium oxide content of the Y-type molecular sieves obtained in the 1 st, 3 rd, 5 th, 7 th and 10 th times was measured by X-ray fluorescence spectrometry, and the obtained results are shown in Table 1.
Example 2
1) And (3) reversely washing an ion exchange column which is in failure of exchanging with the ZSM-5 molecular sieve with deionized water until effluent liquid is clear and free of molecular sieve particles. The ion exchange column was packed with 55mL (dry mass 32 g) of ion exchange resin of the trade name 001X 14.5.
2) Pumping the acid liquor obtained by electrodialysis into the ineffective ion exchange column of 1) from top to bottom by an acid liquor storage tank, wherein the flow rate is 8mL/min, detecting the pH value of effluent liquid in the ion exchange column, stopping acid liquor feeding when the pH value is less than 3, and flushing with deionized water until the pH value is more than 4. The concentration of the acid solution in the acid chamber is 1mol/L.
3) Introducing the salt-containing solution flowing out of the lower end of the ion exchange column in 2) into a waste liquid storage tank. To the above salt-containing solution was added 4g of Na 2 SO 4 And filling the liquid phase into an acid chamber storage tank of the bipolar membrane electrodialysis device, simultaneously adding 1000g of deionized water into an alkali chamber storage tank of the bipolar membrane electrodialysis device, and adding 1000g of 0.25mol/L NaOH solution into an electrode chamber storage tank. Switching on a circulating pump power supply of the bipolar membrane electrodialysis device, starting the circulating pump, starting a direct current power supply between opposite electrodes of the bipolar membrane electrodialysis device after circulation is normal, and regulating voltage to enable current density to be 500A/m 2 Electrodialysis was carried out at 30 ℃.
4) 1000mL of deionized water was added to the beaker, and 100g of ZSM-5 molecular sieve (dry basis) was added thereto, and the molecular sieve slurry was obtained by mechanical stirring. 1.1g Na was added 2 SO 4 As an exchange initiator and preheating to an exchange temperature of 70 ℃;
5) Pumping the obtained molecular sieve slurry into the regenerated ion exchange column 2) from top to bottom, wherein the flow speed is 5mL/min, receiving the flowing molecular sieve slurry below the ion exchange column, sampling 40mL at intervals of 20min, and taking 10 times;
6) And respectively carrying out suction filtration on the molecular sieve slurry samples taken each time, and respectively drying filter cakes at 120 ℃ to obtain 10 parts of ZSM-5 molecular sieve.
The sodium oxide content of the Y-type molecular sieves obtained in the 1 st, 3 rd, 5 th, 7 th and 10 th times was measured by X-ray fluorescence spectrometry, and the obtained results are shown in Table 1.
Example 3
1) And (3) reversely washing an ion exchange column which is failed to exchange with the NaX molecular sieve by deionized water until effluent liquid is clear and free of molecular sieve particles. The ion exchange column was packed with 55mL (dry mass 32 g) of ion exchange resin of the trade name 001X 14.5.
2) Pumping the acid liquor obtained by electrodialysis into the ineffective ion exchange column of 1) from top to bottom by an acid liquor storage tank, wherein the flow rate is 8mL/min, detecting the pH value of effluent liquid in the ion exchange column, stopping acid liquor feeding when the pH value is less than 3, and flushing with deionized water until the pH value is more than 4. The concentration of the acid solution in the acid chamber is 0.9mol/L.
3) Introducing the salt-containing solution flowing out of the lower end of the ion exchange column in 2) into a waste liquid storage tank. Adding 4g of Na to the salt-containing solution 2 SO 4 And filling the liquid phase into an acid chamber storage tank of the bipolar membrane electrodialysis device, simultaneously adding 1000g of deionized water into an alkali chamber storage tank of the bipolar membrane electrodialysis device, and adding 1000g of 0.25mol/L NaOH solution into an electrode chamber storage tank. Switching on a circulating pump power supply of the bipolar membrane electrodialysis device, starting the circulating pump, starting a direct current power supply between opposite electrodes of the bipolar membrane electrodialysis device after circulation is normal, and regulating voltage to enable current density to be 500A/m 2 Electrodialysis was carried out at 30 ℃.
4) 1000mL of deionized water was added to the beaker, and 100g of NaX molecular sieve (dry basis) was added thereto, and mechanically stirred to obtain a molecular sieve slurry. 1.1g Na was added 2 SO 4 As an exchange initiator and preheating to an exchange temperature of 70 ℃;
5) Pumping the obtained molecular sieve slurry into the regenerated ion exchange column 2) from top to bottom, wherein the flow speed is 5mL/min, receiving the flowing molecular sieve slurry below the ion exchange column, sampling 40mL at intervals of 20min, and taking 10 times;
6) And respectively carrying out suction filtration on the molecular sieve slurry samples taken each time, and respectively drying filter cakes at 120 ℃ to obtain 10 parts of NaX molecular sieve.
The sodium oxide content of the Y-type molecular sieves obtained in the 1 st, 3 rd, 5 th, 7 th and 10 th times was measured by X-ray fluorescence spectrometry, and the obtained results are shown in Table 1.
Example 4
1) And (3) reversely washing an ion exchange column which is failed to exchange with the NaY molecular sieve by deionized water until effluent liquid is clear and free of molecular sieve particles. The ion exchange column was packed with 55mL of resin D113.
2) Pumping the acid liquor obtained by electrodialysis into the ineffective ion exchange column of 1) from top to bottom by an acid liquor storage tank, wherein the flow rate is 12mL/min, detecting the pH value of effluent liquid in the ion exchange column, stopping acid liquor feeding when the pH value is less than 3, and flushing with deionized water until the pH value is more than 4. The concentration of the acid solution in the acid chamber is 1mol/L.
3) Introducing the salt-containing solution flowing out of the lower end of the ion exchange column in 2) into a waste liquid storage tank. Adding 4g of Na to the salt-containing solution 2 SO 4 And filling the liquid phase into an acid chamber storage tank of the bipolar membrane electrodialysis device, simultaneously adding 1000g of deionized water into an alkali chamber storage tank of the bipolar membrane electrodialysis device, and adding 1000g of 0.25mol/L NaOH solution into an electrode chamber storage tank. Switching on a circulating pump power supply of the bipolar membrane electrodialysis device, starting the circulating pump, starting a direct current power supply between opposite electrodes of the bipolar membrane electrodialysis device after circulation is normal, and regulating voltage to enable current density to be 500A/m 2 Electrodialysis was carried out at 30 ℃.
4) 1000mL of deionized water was added to the beaker, and 100g of NaY molecular sieve (dry basis) was added thereto, and mechanically stirred to obtain a molecular sieve slurry. 1.1g Na was added 2 SO 4 As an exchange initiator and preheating to an exchange temperature of 70 ℃;
5) Pumping the obtained molecular sieve slurry into the regenerated ion exchange column 2) from top to bottom, wherein the flow speed is 5mL/min, receiving the flowing molecular sieve slurry below the ion exchange column, sampling 40mL at intervals of 20min, and taking 10 times;
6) And respectively carrying out suction filtration on the molecular sieve slurry samples taken each time, and respectively drying filter cakes at 120 ℃ to obtain 10 parts of Y-type molecular sieve.
The sodium oxide content of the Y-type molecular sieves obtained in the 1 st, 3 rd, 5 th, 7 th and 10 th times was measured by X-ray fluorescence spectrometry, and the obtained results are shown in Table 1.
Example 5
1) And (3) reversely washing an ion exchange column which is failed to exchange with the NaY molecular sieve by deionized water until effluent liquid is clear and free of molecular sieve particles. The ion exchange column was packed with 55mL (dry mass 32 g) of a 001X 7 brand ion exchange resin.
2) Pumping the acid liquor obtained by electrodialysis into the failure ion exchange column of 1) from top to bottom by an acid liquor storage tank, wherein the flow rate is 8mL/min, stopping acid liquor feeding when the pH value of effluent liquor in the ion exchange column is less than 6, and the acid liquor concentration in an acid chamber is 0.9mol/L.
3) NH concentration of 0.85mol/L 3 ·H 2 And O alkali liquor is pumped into the ion exchange column 2) from top to bottom, the flow rate is 8mL/min, and when the pH value of effluent liquid in the ion exchange column is detected to be more than 7, the resin can be considered to be completely modified into an ammonium type.
4) Introducing the salt-containing solution flowing out of the lower end of the ion exchange column in 2) into a waste liquid storage tank. To the salt-containing solution was added 4g of Na 2 SO 4 And filling the liquid phase into an acid chamber storage tank of the bipolar membrane electrodialysis device, simultaneously adding 1000g of deionized water into an alkali chamber storage tank of the bipolar membrane electrodialysis device, and adding 1000g of 0.25mol/L NaOH solution into an electrode chamber storage tank. Switching on a circulating pump power supply of the bipolar membrane electrodialysis device, starting the circulating pump, starting a direct current power supply between opposite electrodes of the bipolar membrane electrodialysis device after circulation is normal, and regulating voltage to enable current density to be 500A/m 2 Electrodialysis was carried out at 30 ℃.
5) 1000mL of deionized water was added to the beaker, and 100g of NaY molecular sieve (dry basis) was added thereto, and mechanically stirred to obtain a molecular sieve slurry. 1.1g Na was added 2 SO 4 As exchange initiator, and preheating to 70 deg.c;
6) Pumping the obtained molecular sieve slurry into the regenerated ion exchange column of 3) from top to bottom, wherein the flow speed is 5mL/min, receiving the flowing molecular sieve slurry below the ion exchange column, sampling 40mL at intervals of 20min, and taking 10 times;
7) And respectively carrying out suction filtration on the molecular sieve slurry samples taken each time, and respectively drying filter cakes at 120 ℃ to obtain 10 parts of Y-type molecular sieve.
The sodium oxide content of the Y-type molecular sieves obtained in the 1 st, 3 rd, 5 th, 7 th and 10 th times was measured by X-ray fluorescence spectrometry, and the obtained results are shown in Table 1.
TABLE 1
As can be seen from the data in Table 1, the system provided by the utility model not only realizes the efficient ion exchange of the molecular sieve, but also has no waste gas or waste water emission; meanwhile, the system combines the regeneration process of the ion exchange column with the bipolar membrane electrodialysis device, so that the recycling of the regeneration liquid is realized, and the byproduct sodium hydroxide is produced.
The preferred embodiments of the present utility model have been described in detail above, but the present utility model is not limited thereto. Within the scope of the technical idea of the utility model, a number of simple variants of the technical solution of the utility model are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the utility model, all falling within the scope of protection of the utility model.
Claims (7)
1. A system for preparing a molecular sieve in hydrogen form, the system comprising: the pulping tank, the ion exchange column filled with resin and the bipolar membrane electrodialysis device are sequentially connected, and the slurry storage tank, the waste liquid storage tank and the acid liquid storage tank are sequentially connected;
A three-way valve is arranged above the ion exchange column, and a first inlet, a first outlet and a second inlet in the three-way valve are respectively connected with the beating tank, the ion exchange column and the acid liquid storage tank; the bottom of the ion exchange column is provided with a double-port valve, a second outlet and a third outlet in the double-port valve are respectively connected with the slurry storage tank and the waste liquid storage tank, and the bottom and the top of the ion exchange column are respectively provided with a flushing fluid inlet and a flushing fluid outlet, and can be controlled to perform an exchange process, a back flushing process and a regeneration process in the same ion exchange column.
2. The system of claim 1, wherein the waste reservoir is disposed on a bottom of the ion exchange column and a connecting conduit of the bipolar membrane electrodialysis device;
the acid liquor storage tank is arranged on a second inlet of the three-way valve and a connecting pipeline of the bipolar membrane electrodialysis device.
3. The system of claim 2, wherein the first inlet, the second inlet, the first outlet, the second outlet, the third outlet, the rinse inlet, and the rinse outlet each independently have an operational state and a closed state.
4. A system according to any one of claims 1 to 3, wherein the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with counter electrodes, at least two bipolar membranes and at least one cation exchange membrane which are arranged between the counter electrodes, and the bipolar membranes and the cation exchange membranes are alternately arranged;
Wherein an acid chamber is formed between the cation exchange layer and the cation exchange membrane in the bipolar membrane; an alkali chamber is formed between the anion exchange layer and the cation exchange membrane in the bipolar membrane; an electrode chamber is formed between the counter electrode and the bipolar membrane.
5. A system according to any one of claims 1 to 3, wherein the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with a counter electrode, at least two bipolar membranes and at least one anion exchange membrane which are arranged between the counter electrodes, and the bipolar membranes and the anion exchange membranes are alternately arranged;
wherein an acid chamber is formed between the cation exchange layer and the anion exchange membrane in the bipolar membrane; an alkali chamber is formed between the anion exchange layer and the anion exchange membrane in the bipolar membrane; an electrode chamber is formed between the counter electrode and the bipolar membrane.
6. A system according to any one of claims 1 to 3, wherein the bipolar membrane electrodialysis device comprises: the electrode frame is internally provided with counter electrodes, at least two bipolar membranes, at least one group of cation exchange membranes and anion exchange membranes, which are adjacently arranged, are arranged between the counter electrodes, and the cation exchange membranes and the anion exchange membranes are alternately arranged with the bipolar membranes;
Wherein a salt chamber is formed between the cation exchange membrane and the anion exchange membrane; an acid chamber is formed between the cation exchange layer and the anion exchange membrane in the bipolar membrane, and an alkali chamber is formed between the anion exchange layer and the cation exchange membrane in the bipolar membrane; the counter electrode and bipolar membrane form an electrode chamber.
7. The system of claim 2, wherein the rinse liquid outlet is connected to the beater tank.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202320008447.8U CN219991243U (en) | 2023-01-03 | 2023-01-03 | System for preparing hydrogen type molecular sieve |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202320008447.8U CN219991243U (en) | 2023-01-03 | 2023-01-03 | System for preparing hydrogen type molecular sieve |
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