CN116426942B - Device and method for preparing bromine and hydrogen by integrating PTA incineration ash and slag through electrolytic rectification - Google Patents
Device and method for preparing bromine and hydrogen by integrating PTA incineration ash and slag through electrolytic rectification Download PDFInfo
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- CN116426942B CN116426942B CN202310693672.4A CN202310693672A CN116426942B CN 116426942 B CN116426942 B CN 116426942B CN 202310693672 A CN202310693672 A CN 202310693672A CN 116426942 B CN116426942 B CN 116426942B
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- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 162
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 89
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 22
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract 18
- 239000002893 slag Substances 0.000 title claims description 7
- 239000012528 membrane Substances 0.000 claims abstract description 95
- 238000005341 cation exchange Methods 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 44
- 239000003011 anion exchange membrane Substances 0.000 claims abstract description 38
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000001301 oxygen Substances 0.000 claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 15
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003546 flue gas Substances 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 72
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 23
- 230000005494 condensation Effects 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 23
- 238000002425 crystallisation Methods 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 21
- 238000005868 electrolysis reaction Methods 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 16
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 14
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 230000036961 partial effect Effects 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000010413 mother solution Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000005192 partition Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000004062 sedimentation Methods 0.000 claims description 3
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002253 acid Substances 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 17
- 239000001569 carbon dioxide Substances 0.000 abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 9
- 239000002351 wastewater Substances 0.000 abstract description 9
- 239000006227 byproduct Substances 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 3
- 150000002484 inorganic compounds Chemical class 0.000 abstract 1
- 229910010272 inorganic material Inorganic materials 0.000 abstract 1
- -1 bromine ions Chemical class 0.000 description 27
- 239000012071 phase Substances 0.000 description 15
- 239000010410 layer Substances 0.000 description 9
- 238000006722 reduction reaction Methods 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 230000002829 reductive effect Effects 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- 239000000428 dust Substances 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 159000000000 sodium salts Chemical class 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000005349 anion exchange Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- ZWLPBLYKEWSWPD-UHFFFAOYSA-N o-toluic acid Chemical compound CC1=CC=CC=C1C(O)=O ZWLPBLYKEWSWPD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- HVAAVHPGMBVROG-UHFFFAOYSA-L [Br-].[Na+].C([O-])(O)=O.[Na+] Chemical compound [Br-].[Na+].C([O-])(O)=O.[Na+] HVAAVHPGMBVROG-UHFFFAOYSA-L 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical group 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Chemical class [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- 239000008364 bulk solution Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000013526 supercooled liquid Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/24—Halogens or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
- C25B9/21—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms two or more diaphragms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The application relates to the technical field of nonmetallic element and inorganic compound preparation, in particular to a device and a method for preparing bromine and hydrogen by electrolytic rectification of PTA incineration ash. The device comprises an integrated annular electrolytic rectifying tower, wherein the integrated annular electrolytic rectifying tower comprises an electrolytic tower kettle section at the lower part and a rectifying section at the upper part, and the lower part of the rectifying section stretches into the electrolytic tower kettle section; the electrolytic tower kettle section sequentially comprises a cathode, a bipolar membrane, a cation exchange membrane and an anion exchange membrane which are concentrically and annularly arranged from outside to inside, wherein the inside of the anion exchange membrane is an anode. The application realizes the resource utilization of PTA waste water incineration ash waste, the electrolytic rectification integrated device realizes the in-situ direct separation of electrolytic product bromine, removes low-conductivity bromine to improve the electrolytic stability, effectively inhibits the oxygen evolution reaction, does not need additional acid, saves the running cost, prepares high-value products such as bromine, hydrogen and the like, and simultaneously produces alkali liquor as a byproduct, which can absorb carbon dioxide in incineration flue gas and reduce the discharge amount of carbon dioxide.
Description
Technical Field
The application relates to the technical field of nonmetallic element preparation, in particular to a device and a method for preparing bromine and hydrogen by electrolytic rectification of PTA incineration ash.
Background
The waste water produced in the PTA production process contains mostly organic matters such as phthalic acid, paraxylene, methylbenzoic acid, phthalic acid, benzoic acid, methyl acetate, 4-CBA, acetic acid and the like, and inorganic matters such as sodium, cobalt, manganese, bromine and the like. The organic matters and inorganic matters can produce ash slag at the bottom of the hearth and the outlet of the bag-type dust collector after being burnt at high temperature. The main components in the ash are sodium carbonate, sodium bromide and a small amount of metal oxide, and the recycling value is high.
After the ash is dissolved, sodium carbonate and sodium bromide can be separated by methods such as evaporation crystallization, cooling crystallization and the like, but the purity is not high and the value is greatly reduced. If sodium bromide is converted into bromine for separation, the influence of sodium carbonate on the purity of bromine element is avoided, and the value of the recovery product can be further improved. Bromine is used as an important fine chemical basic raw material, can be used for producing various bromides, bromates and bromine-containing organic compounds required by industry, and is widely applied to the fields of high-efficiency flame retardants, refrigerants, petroleum completion liquids, medicines, fuel intermediates, chemical reagents and the like. More than 4500 bromine compounds are synthesized artificially at present, and with further development of science and technology, more applications of bromine can be realized.
Prior art publication No.: CN113789525a, name: the technological process of producing bromine by electrolytic acidification of sodium bromide includes the steps of electrolyzing acidified sodium bromide solution to produce bromine, dissolving the bromine in the acidified sodium bromide solution to form mixed liquid, distilling in bromine distilling tower and evaporating bromine in bromine distilling tower. The process method takes sodium bromide as a raw material, and abandons the preparation of bromine by oxidation of chlorine, but needs continuous addition of acid liquor to maintain pH, and has high production and operation cost. If the sodium salt system of the ash is burned by the PTA waste liquid, more acid liquid is consumed and the high-value sodium salt is converted into low-value sodium salt after electrolysis because the solution is an alkaline system.
Prior art publication No.: CN111285330a, name: a process for preparing hydrobromic acid by bipolar membrane electrodialysis method includes such steps as alternatively combining bipolar membrane, cation exchange membrane and anion exchange membrane to obtain membrane stack, and applying DC power to both sides of membrane stack to obtain H 2 O is electrolyzed in the middle layer of the bipolar membrane to H+ and OH-, and H+ migrates through the cation exchange membrane to the cathode into the acid compartment, br-in the salt compartment also enters the acid compartment through the anion exchange membrane, whereby in the acidHBr is generated in the chamber; OH "migrates to the anode through the anion exchange membrane and enters the base compartment, and na+ in the salt compartment also enters the base compartment through the cation exchange membrane, thereby generating NaOH in the base compartment. The acid chamber near the anode forms an alkaline environment in the anode while the bipolar membrane is in acid production by water dissociation, and bromine ions are blocked by the bipolar membrane near the anode, so that only oxygen evolution reaction occurs in the anode, and the electrolytic reaction occurring at the anode and the cathode is actually an electrolytic water reaction.
Disclosure of Invention
Aiming at the technical problems existing in the prior art, the application discloses a device and a method for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash, and the device does not need to additionally add acid liquor, is suitable for an alkaline system of PTA sodium salt, reduces the separation requirement of the front end on sodium carbonate, can separate bromine and hydrogen in situ, integrally realizes the preparation and separation process, realizes the recycling utilization of the incineration ash, and has high economic value.
On one hand, the application provides a device for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash, which comprises an annular electrolytic rectifying tower, wherein the annular electrolytic rectifying tower comprises a lower electrolytic tower kettle section and an upper rectifying section, and the lower part of the rectifying section stretches into the electrolytic tower kettle section; the electrolytic tower kettle section sequentially comprises a cathode 1, a bipolar membrane 2, a cation exchange membrane 3 and an anion exchange membrane 4 which are concentrically and annularly arranged from outside to inside, wherein an anode 5 is arranged in the anion exchange membrane 4, the bipolar membrane 2, the cation exchange membrane 3, the anion exchange membrane 4 and the bottom of the annular electrolytic rectifying tower are in sealed connection, the bipolar membrane 2 is formed by compounding the cation exchange membrane and the anion exchange membrane, and the cation exchange membrane of the bipolar membrane 2 is arranged at the side close to the cathode 1; the upper part of the cation exchange membrane 3 is connected with the bottom of the side wall of the rectifying section in a sealing way, the upper part of the anion exchange membrane 4 is connected and sealed with the inner wall of the rectifying section by an inclined plate for the liquid of the rectifying section to slide down, a feeding chamber is formed between the cation exchange membrane 3 and the anion exchange membrane 4, a cathode chamber is formed between the cathode 1 and the bipolar membrane 2, an alkali chamber is formed between the bipolar membrane 2 and the cation exchange membrane 3, a cation chamber is formed between the anode 5 and the anion exchange membrane 4, and an empty chamber is formed outside the cation exchange membrane 3 and above the cathode 1 and the bipolar membrane 2.
In particular, the top of the annular electrolytic rectifying tower is connected with the top of the condensation separator 8, water separated by the condensation separator 8 is returned to the electrolytic rectifying tower, and separated non-condensable gas is returned to the lower part of the rectifying section to maintain the partial pressure of electrolytic oxygen to be more than 10kPa.
Particularly, a crystallization separation unit is arranged in front of the annular electrolytic rectifying tower and comprises a dissolution filtering device, an evaporation crystallization device and a centrifugal separation device which are sequentially connected, and the centrifugal separation device is connected with the annular electrolytic rectifying tower.
In particular, the operating pressure of the rectifying section is between 20 and 101kPa, the operating temperature of the top plate of the tower is between 50 and 93 ℃, and the reflux ratio is preferably between 0.5 and 5.
Particularly, an alkali chamber of the electrolytic tower kettle section is connected with a flue gas absorption tower, and absorption liquid of the flue gas absorption tower is sent into an evaporation crystallization device; and delivering the crystals separated by the centrifugal separation device to a drying device, and delivering the mother liquor separated by the centrifugal separation device to a feeding chamber.
On the other hand, the application also provides a method for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash, which comprises the steps of sodium carbonate crystallization separation, electrolytic bromine preparation and rectification separation, wherein the device is used for dissolving ash, filtering to remove insoluble metal oxide impurities, evaporating filtrate for crystallization, crystallizing 85% -95% of sodium carbonate after evaporation, centrifuging, and delivering the centrifuged mother liquor into a feeding chamber of an electrolytic tower kettle section for electrolysis; a cathode chamber is arranged between the cathode and the bipolar membrane, hydrogen is generated in the cathode chamber, and the hydrogen is sent out after gas-liquid sedimentation separation in the air chamber; an alkali chamber is formed between the bipolar membrane and the cation exchange membrane, wherein NaOH is generated; the sectional area of a positive chamber formed between the anode 5 and the anion exchange membrane 4 is at least 25% of the sectional area of the bottom section of the electrolytic tower, bromine is generated, and the bromine is evaporated in situ after heating and leaves the positive chamber liquid phase.
In particular, the vapour leaving the liquid phase of the cation chamber enters the rectifying section, the gas flow passing out from the top of the rectifying section is then passed in from the upper part of the condensation separator 8, and the non-condensable gas in the condensation separator 8 is returned to the lower part of the rectifying section to maintain the partial pressure of the electrolytic oxygen greater than 10kPa.
Particularly, the condensation separator 8 adopts water cooling, the heat exchange mode of the condensation separator 8 adopts partition wall condensation, the operating pressure of the rectifying section is 20 kPa-101 kPa, the operating temperature of the top of the rectifying section is 50-93 ℃, and the reflux ratio is 0.5-5.
Specifically, the ash is dissolved to obtain a solution with the mass fraction of 20% -25%, filtrate is evaporated and sodium carbonate is centrifugally separated to obtain a centrifugal mother solution; the mass concentration of sodium bromide in the feeding solution fed into the feeding chamber is 20% -50% and the mass concentration of sodium carbonate is 1% -10%.
In particular, the electrolysis voltage between the anode and the cathode is 1.2V-3V, the temperature of the kettle section of the electrolysis tower is 60-100 ℃, and the partial pressure of the electrolytic oxygen is more than 10kPa.
On the basis of the common sense in the art, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the application.
The technical scheme has the following advantages or beneficial effects: the application realizes the resource utilization of PTA waste water incineration ash waste, the electrolytic rectification integrated device realizes the in-situ direct separation of electrolytic product bromine, removes low-conductivity bromine, improves the electrolytic stability, reduces the ion concentration in the electrolyte, and promotes the hydrolysis equilibrium of the bipolar membrane interlayer to be continuously carried out in the dissociation direction. The oxygen partial pressure is maintained, so that the oxygen evolution reaction is effectively inhibited, additional acid is not needed, and the operation cost is saved. The application prepares high value products such as bromine, hydrogen and the like, and simultaneously, sodium hydroxide alkali liquor is also byproduct, which can further absorb carbon dioxide generated during fixed incineration and return to the sodium carbonate crystallization separation process section. Of course, not all of the advantages described above are necessarily achieved at the same time by any one of the solutions of the application.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It will be obvious to a person skilled in the art that other figures can be obtained from the figures provided without the inventive effort.
FIG. 1 is a schematic illustration of a process flow principle according to one embodiment of the application.
Fig. 2 is a schematic view of an electrolytic rectifying column structure according to one embodiment of the present application.
FIG. 3 is a schematic cross-sectional view of an electrolytic rectification column bottom according to one embodiment of the present application.
Fig. 4 is a schematic view of an electrolysis principle according to an embodiment of the present application.
Wherein, 1-cathode, 2-bipolar membrane, 3-cation exchange membrane, 4-anion exchange membrane, 5-anode, 6-tower outer wall, 7-rectifying tower plate and 8-condensing separator.
Detailed Description
The technical solutions in the embodiments of the present application are clearly and completely described below with reference to the accompanying drawings. It is obvious that the described embodiments are only some of the embodiments of the present application and are intended to explain the inventive concept. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to fall within the scope of the application.
The terms "center," "longitudinal," "transverse," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "axial," "radial," "circumferential," and the like as used in the description are based on the orientation or positional relationship shown in the drawings and are merely for simplicity of description and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operate in a particular orientation.
The terms "coupled," "connected," and the like as used in the description herein are to be construed broadly and may be, for example, fixedly coupled, detachably coupled, or integrally formed, unless otherwise specifically defined and limited; may be a mechanical connection, an electrical connection; can be directly connected and indirectly connected through an intermediate medium; may be a communication between two elements or an interaction between two elements. The specific meaning of the terms in the embodiments can be understood by those of ordinary skill in the art according to the specific circumstances.
Unless expressly stated or limited otherwise, a first feature "above," "below," or "above" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "above," "over" or "on" a second feature may be a first feature being directly above or obliquely above the second feature, or simply indicating that the first feature is level higher than the second feature. A first feature "under", "beneath" or "under" a second feature may be either the first and second features in direct contact, or the first and second features in indirect contact via an intervening medium. Moreover, a first feature being "under", "beneath" or "under" a second feature may be a first feature being directly under or diagonally under the second feature, or simply indicating that the first feature is less level than the second feature.
The terms "one particular embodiment" and "one particular embodiment" as used in this description mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the application. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
Referring to fig. 1, a specific embodiment of the application provides a method for preparing bromine and hydrogen by electrolytic rectification of PTA incineration ash, which comprises three processes of sodium carbonate crystallization separation, electrolytic bromine preparation and rectification separation. The sodium carbonate crystallization separation comprises the steps of collecting ash residues at the bottom of an incineration hearth, an outlet of a bag-type dust collector and the like after the PTA wastewater is incinerated; dissolving the mixture into a solution with the mass fraction of 20-25% in a dissolving and filtering unit, and filtering to remove insoluble metal oxide impurities to obtain filtrate; introducing the filtrate into an evaporation crystallization unit, and crystallizing 85% -95% of sodium carbonate to form crystal slurry after the moisture in the solution is evaporated; treating the crystal slurry by a centrifugal separation unit to obtain crystals and mother liquor; and removing the crystals from the drying unit to obtain a high-purity sodium carbonate product. The electrolytic bromine preparation and rectification separation comprises the steps that centrifugal residual mother liquor enters an electrolytic rectification tower to generate electrolytic bromine preparation and hydrogen reaction, bromine is discharged from the top of the tower and enters a condensation liquid separation unit, and the electrolytic rectification tower can feed and discharge under an alkaline system and can realize in-situ rectification separation bromine extraction.
Referring to fig. 2 to 4, an embodiment of the present application proposes an apparatus for producing bromine and hydrogen by electrolytic rectification of PTA incineration ash, the apparatus comprising an annular electrolytic rectification column and a cooperative condensation separator 8, the annular electrolytic rectification column comprising an electrolytic column kettle section and a rectification section from bottom to top, and the lower part of the rectification section extending into the electrolytic column kettle section. The typical structure of the electrolytic tower kettle section is that a cathode-bipolar membrane-cation exchange membrane-anion exchange membrane-anode are sequentially arranged from outside to inside, and the anion exchange membrane 4, the cation exchange membrane 3, the bipolar membrane 2 and the cathode 1 are all arranged in concentric annular shapes. The upper part of the cation exchange membrane 3 is connected with the bottom of the side wall of the rectifying section in a sealing way, the upper part of the anion exchange membrane 4 is connected with the inner wall of the rectifying section by a bevel board, and a feeding chamber is formed between the cation exchange membrane 3 and the anion exchange membrane 4. The outside of the cation exchange membrane 3 and the upper parts of the cathode 1 and the bipolar membrane 2 are provided with a hollow chamber for temporarily storing the hydrogen generated by the cathode 1 and carrying out gas-liquid separation. The anode and cathode combined type electrolytic tower comprises a cation exchange membrane 3, an anion exchange membrane 4, a bipolar membrane 2 and a kettle bottom of the electrolytic tower kettle section, wherein the bipolar membrane 2 is formed by compounding the cation exchange membrane and the anion exchange membrane, the cation exchange membrane of the bipolar membrane 2 is arranged towards the cathode 1, and the anion exchange membrane of the bipolar membrane 2 is arranged towards the anode 5.
The residual mother liquor after centrifugation enters the electrolytic tower kettle section from the feeding chamber, and the inclined panel separates the feeding chamber from the rectifying section to prevent condensed bromine vapor from entering the feeding chamber and simultaneously prevent bromine condensate from accumulating at the top of the feeding chamber. A cathode chamber is formed between the cathode and the bipolar membrane, hydrogen is generated by electrolysis, and the generated hydrogen can be sent out after gas-liquid sedimentation and separation at a certain height in the air chamber. An alkali chamber is formed between the bipolar membrane and the cation exchange membrane, and the dissociated hydroxide ions and sodium ions passing through the cation exchange membrane form NaOH solution to be sent out. The cross-sectional area of a positive chamber formed between the anode 5 and the anion exchange membrane 4 is at least 25% of the cross-sectional area of the bottom section of the electrolytic tower, and the part maintains an acidic environment to inhibit oxygen evolution reaction, bromine is generated therefrom, a positive chamber product is heated and evaporated in situ, the bromine is separated from a positive chamber liquid phase, the electrolytic reaction is prevented from being inhibited due to the existence of a difficult conductive bromine liquid phase, and the positive chamber electrolysis is promoted. The area of the cation chamber is maximized as much as possible, and the realization of in-situ separation of bromine is further ensured. And (3) leading out sodium hydroxide alkali liquor serving as a byproduct to a carbon dioxide alkali washing tower, absorbing carbon dioxide in flue gas from an outlet of the PTA wastewater incineration boiler, controlling the pH value of an absorption liquid at an outlet of the absorption tower to 12 to generate sodium carbonate solution, removing the sodium carbonate solution from an evaporation crystallization unit, recycling sodium carbonate, and discharging the absorbed flue gas through a chimney.
The rectifying section can be provided with a plate rectifying tower or a packed rectifying tower and the like, the operating pressure of the rectifying section is between 20 and 101kPa, the operating temperature of the tower top is between 50 and 93 ℃, and the reflux ratio is preferably between 0.5 and 5. Preferably, the trays are provided with cofferdams to reduce liquid phase reflux of the bromine phase. The feeding thermal state of the application is supercooled liquid or bubble point feeding, the separated light components are generated in situ in the tower kettle, the heating distillation rate of the rectifying section is limited by the product generation rate of the electrolytic section, the bromine generated in situ is separated from the liquid phase of the tower kettle in situ at the same time, the stable operation of the electrolytic device is promoted, and the rectifying section and the electrolytic section form an organic synergistic and mutual promotion relationship. In addition, the electrolytic rectifying tower has no stripping section in the rectifying section, but different from batch rectifying, the electrolytic rectifying tower can continuously feed, electrolyze and discharge.
The condensation separator 8 adopts water cooling, the heat exchange mode adopts partition wall condensation, steam enters from the upper part of the condensation separator 8, and Br is utilized 2 And H 2 O is subjected to preliminary separation on a heat exchange surface in different condensation sequences, bromine dew point is low, and H is the later 2 O condenses in the lower part of the heat exchange surface, which is similar to Br 2 /H 2 The specific gravity delamination position of O is the same. The lower part of the device is provided with a condensate separating tank, the inside of the device is provided with a cofferdam baffle plate, and Br is further treated by utilizing density difference 2 And H 2 O separation, namely bromine phase with larger specific gravity than water phase, layering, namely bromine phase on the lower layer of liquid phase, and forming the water phase by two processes of condensation separation and specific gravity separationBetter Br 2 /H 2 O separation effect. The water phase is extracted from the upper part of the condensate separating tank after overflow of the cofferdam baffle, the bromine phase is extracted from the lower part, the water phase reflux port is provided with a baffle to prevent the bromine phase condensed on the lower part of the lower heat exchange surface from reflux into the rectifying tower again, and the non-condensable gas outlet is provided with a baffle to prevent liquid drops from being entrained.
In order to further improve the electrolysis efficiency and reduce the occurrence of the anodic oxygen evolution reaction, noncondensable gases such as oxygen and the like in the condensation separator 8 are returned to the lower part of the rectifying section, namely the upper part of the electrolysis section, so as to maintain the partial pressure of the electrolytic oxygen to be more than 10kPa, thereby inhibiting the occurrence of the anodic side reaction. The design of the condensation separator ensures that the water phase flows back into the electrolytic rectifying tower, the loss of bromide ions and water elements is reduced, the oxygen flows back to maintain partial pressure so as to reduce the energy consumption of electrolytic side reaction, the concentration of NaOH as a product is improved, the better separation effect of bromine reduces the energy consumption loss caused by the reflux of bromine into the rectifying tower, and the condensation separator and the electrolytic rectifying tower have a synergistic effect.
Preferably, the electrolysis voltage between the cathode and the anode of a typical electrolysis structure is between 1.2 and 3V. The cation chamber maintains a pH < 2.8. The mass concentration of sodium bromide in the feeding solution of the material chamber is 20-50%, and the mass concentration of sodium carbonate is 1-10%. The operation temperature of the kettle section of the electrolytic tower is 60-100 ℃.
The technical principle related by the application is specifically described as follows, sodium carbonate is separated by crystallization: at the same temperature, sodium carbonate has a lower solubility in water than sodium bromide. By utilizing the characteristic that the sodium carbonate ratio in the PTA incineration ash is higher than that of sodium bromide, the concentration of sodium carbonate is concentrated to be higher than the saturation concentration by adopting evaporation crystallization, sodium carbonate is preferentially crystallized and separated out, and sodium bromide is enriched and concentrated in a liquid phase. Controlling the concentration of the concentrate to below the sodium carbonate-sodium bromide eutectoid point allows for a smaller amount of sodium carbonate to remain in the concentrated sodium bromide solution.
Preparing bromine by electrolysis: the direct current passes through the concentrated alkaline sodium bromide solution to cause the electrolyte to react chemically on the electrodes, converting the electrical energy into chemical energy. When the power is on, hydrogen ions in the electrolyte move to the cathode to absorb electrons, and a reduction reaction is carried out to generate hydrogen; the anions in the electrolyte move to the anode to release electrons, and oxidation reaction occurs. Phi under alkaline condition θ O2/OH- =0.401V，φ θ Br2/Br- =1.065V，O 2 Is lower than Br 2 The anode will mainly produce oxygen evolution reaction under acidic condition phi θ O2/H2O = 1.229V, according to the Nernst equation, O 2 Will increase with decreasing pH, when Br - The oxidation reaction of the ions will become the main reaction, so that the formation of bromine elementary substance is favored under the acidic condition, and the theoretical dominant transition point is ph=2.8.
The reaction equations involved in the cell include the anodic main reaction: 2Br - -2e - →Br 2 The method comprises the steps of carrying out a first treatment on the surface of the Anode side reaction: 2H (H) 2 O-4e - →O 2 ↑+4H + The method comprises the steps of carrying out a first treatment on the surface of the Cathode reaction: 2H (H) + +2e - →H 2 And ≡. For the sodium salt system of the PTA incineration ash, as the solution presents alkalinity, the oxygen evolution reaction is dominant, the reduction of bromide ions is not facilitated, and acid is continuously added for directly electrolyzing bromine, wherein part of acid is consumed by sodium carbonate in a liquid phase, the main acid maintains the pH of the liquid phase to ensure the reduction of bromide ions, and the general reaction equation is as follows (HA represents acid): 2NaBr+2HA→2NaA+H 2 +Br 2 。
Aiming at the problems, the application utilizes an electrolytic cell designed by a bipolar membrane and an anion/cation exchange membrane to realize the electrolysis of sodium bromide under the condition of not consuming acid, and realizes the reaction equation as follows: 2NaBr+2H 2 O→2NaOH+H 2 +Br 2 . The anion/cation exchange membrane is capable of allowing specific charged ions in solution to pass through while blocking other charged ions and electrically neutral species. The structure of the ion-exchange polymer mainly comprises a polymer main chain, a fixed group on the main chain and movable ions. Depending on the fixed ionic groups of the ion exchange membrane, they may be referred to as cation exchange membranes and anion exchange membranes, respectively. The cation exchange membrane can selectively allow cations to pass through and block anions. Whereas anion exchange membranes are usually prepared from positively charged polyelectrolytes, the anchoring groups are typically quaternary amine, imidazole, etc., attracting negatively charged ions, rejecting positively charged ions, thus selectively allowing anions to pass, blocking cations. Bipolar membrane: a membrane formed by compounding a cation exchange membrane and an anion exchange membrane, wherein an intermediate layer between the two composite membranes is a water layer, and when the bipolar membrane is reversely pressurized, H in the water layer 2 Cleavage of O to H + And OH (OH) - And migrate through the cation exchange membrane and the anion exchange membrane, respectively, to the bulk solution.
By utilizing the characteristics of the membrane, the application designs an electrolytic structure shown in figure 4, sodium ions and bromide ions of sodium bromide are respectively migrated to the cathode and anode through the anion-cation exchange membrane under the action of an electric field, the cathode side adopts the bipolar membrane to promote dissociation of water molecules, the water molecules outside the bipolar membrane 2 permeate into the bipolar membrane 2, and the water molecules are dissociated into hydrogen ions and hydroxide ions on the interface between the cation exchange membrane and the anion exchange membrane of the bipolar membrane 2; hydrogen ions can pass through the cation exchange membrane to enter the cathode chamber, but the hydrogen ions are blocked by the anion exchange membrane and cannot enter the anode chamber, the dissociated hydrogen ions are reduced on the cathode to prepare hydrogen, and dissociated OH - NaOH is generated with sodium ions. Similarly, hydroxide ions pass through the anion exchange membrane and sodium ions passing through the cation exchange membrane 3 to generate sodium hydroxide, and hydroxide ions are blocked by the cation exchange membrane, so that synchronous progress of the oxidation reaction of bromide and the reduction reaction of hydrogen ions without adding acid liquid can be ensured.
On the anode side, hydroxide ions in the solution undergo oxidation reaction at the anode 5 to precipitate oxygen and continuously generate hydrogen ions. At a theoretical advantage transition point of ph=2.8, the oxygen evolution reaction is stopped while maintaining an acidic environment by the barrier of the ion exchange membrane, so that reduction of bromide ions occurs on the anode. Because the hydrogen under the electrolytic structure of the application is derived from hydrogen ions dissociated by water molecules, naOH is generated as a product, and acid is not consumed additionally, the electrolytic structure of the application can realize the electrolytic preparation of bromine by sodium bromide without acid consumption, and simultaneously effectively inhibit oxygen evolution reaction.
And (3) rectifying and separating: a separation process for separating components by utilizing the difference in volatility of the components in a mixture. Rectification is usually carried out in a rectifying tower, and gas-liquid two phases are in countercurrent contact to carry out phase-to-phase heat and mass transfer. The volatile components in the liquid phase enter the gas phase, and the less volatile components in the gas phase are transferred to the liquid phase, so that almost pure volatile components can be obtained at the top of the tower and almost pure less volatile components can be obtained at the bottom of the tower. And condensing vapor led out from the top of the tower, wherein a part of condensate is used as reflux liquid and returns to the rectifying tower from the top of the tower, and the rest distillate is the top product. The liquid extracted from the bottom of the tower is gasified by the reboiler, the vapor rises along the tower, and the rest liquid is used as the bottom product. The ratio of the amount of liquid flowing back into the column at the top of the column to the amount of product at the top of the column is called reflux ratio, and its size affects the separation effect and energy consumption of the rectification operation.
Bromine has strong volatility at normal pressure, the boiling point is 58.8 ℃ and the difference between the boiling point and the boiling point of water is large, and the solubility of bromine in water is small. After bromine simple substance is prepared by electrolysis, bromine can be separated from liquid phase in situ by rectification, so that further electrolytic reaction is promoted, and the influence of generated bromine on the reduction of the conductivity of the electrolytic cell is reduced. Therefore, the application designs the electrolytic structure into an annular structure, and can realize the in-situ rectification and bromine separation of the electrolyte phase. And meanwhile, when bromine vapor and water vapor are condensed at the top of the rectifying tower, the water vapor is firstly condensed, bromine vapor is condensed, the density of bromine is higher than that of water, and the condensing device is designed to realize the separation of bromine and water in the condensing process.
Example 1
Cooling and dissolving ash at the bottom of the PTA waste water incineration hearth and the outlet ash of the bag-type dust collector in a slag dissolving tank until the mass fraction is 20-25%, the temperature is 60-80 ℃, filtering to remove insoluble metal oxide, and then entering an evaporation crystallizer for evaporation and crystallization at the temperature of 80-90 ℃ and the evaporation pressure of 50-70 kpa. And (3) centrifuging the evaporated crystal slurry in a centrifuge, drying the centrifuged crystal to obtain a sodium carbonate product, wherein 1000kg/h of a centrifuging mother solution contains about 40% of sodium bromide, and 5% of sodium carbonate enters the bottom of the electrolytic rectification tower from between the cation exchange membrane 3 and the anion exchange membrane 4. The electrolysis voltage is designed to be 1.6V, the electrolysis temperature is 60 ℃, under the action of direct current, hydroxide ions in the solution are subjected to oxidation reaction at the anode 5 to separate out oxygen and continuously generate hydrogen ions, and when the pH of the anolyte is reduced to about 2.8, the oxygen separation reaction is stopped, and bromine starts to be generated. Simultaneously, the bipolar membrane 2 continuously dissociates hydroxide ions and hydrogen ions, wherein the hydroxide ions and sodium ions passing through the cation exchange membrane 3 produce sodium hydroxide, and the hydrogen ions undergo a reduction reaction at the cathode 1 to produce hydrogen. The anolyte is introduced into a thermosiphon reboiler and heated to about 60 ℃ to partially vaporize and then reflux into the column. The operating pressure of the rectifying section is designed to be 30kPa, bromine steam rises to the top of the tower and is layered after being condensed by a condenser at the condensation temperature of 50 ℃, the reflux ratio of water and a small amount of bromine in the upper layer to the inside of the tower is 2, the bromine product is produced in the lower layer, and the bromine yield is 280kg/h. The hydrogen produced by the cathode 1 was sent to a hydrogen tank after being washed by a water scrubber, and the hydrogen yield was 3.5kg/h. The 716kg/h of the tower bottom byproduct 20wt% sodium hydroxide alkali liquor is led out to a carbon dioxide alkali washing tower to absorb the carbon dioxide with the concentration of 8-11% in the flue gas from the outlet of the PTA waste water incineration boiler, the temperature is lower than 110 ℃, the pH value of the absorption liquid at the outlet of the absorption tower is controlled to 12 to generate sodium carbonate solution, the sodium carbonate solution is recovered by an evaporation crystallization unit, and the absorbed flue gas is discharged through a chimney.
Example 2
Cooling and dissolving ash at the bottom of the PTA waste water incineration hearth and the outlet ash of the bag-type dust collector in a slag dissolving tank until the mass fraction reaches 20-25% and the temperature reaches 60-80 ℃, filtering to remove insoluble metal oxides, and then entering an evaporation crystallizer for evaporating and crystallizing at the evaporating temperature of 80-90 ℃ and the evaporating pressure of 50-70 kpa. And (3) centrifuging the evaporated crystal slurry in a centrifuge, drying the centrifuged crystal to obtain a sodium carbonate product, wherein 1000kg/h of a centrifuging mother solution contains about 50% of sodium bromide, and 1% of sodium carbonate enters the bottom of the electrolytic rectification tower from between the cation exchange membrane 3 and the anion exchange membrane 4. The electrolysis voltage is designed to be 1.4V, the electrolysis temperature is 85 ℃, under the action of direct current, hydroxide ions in the solution are subjected to oxidation reaction at the anode 5 to separate out oxygen and continuously generate hydrogen ions, and when the pH of the anolyte is reduced to about 2.8, the oxygen separation reaction is stopped, and bromine starts to be generated. Simultaneously, the bipolar membrane 2 continuously dissociates hydroxide ions and hydrogen ions, wherein the hydroxide ions and sodium ions passing through the cation exchange membrane 3 produce sodium hydroxide, and the hydrogen ions undergo a reduction reaction at the cathode 1 to produce hydrogen. The anolyte was introduced into a thermosiphon reboiler heated to about 85 ℃ to partially vaporize and then returned to the column. The operating pressure of the rectifying section is designed to be 60kPa, bromine steam rises to the top of the tower to be condensed by a condenser at the condensing temperature of 78 ℃ and then is layered, the reflux ratio of water and a small amount of bromine in the upper layer to the tower is 2, the bromine product is produced in the lower layer, and the bromine yield is 350kg/h. The hydrogen produced by the cathode 1 was sent to a hydrogen storage tank after being washed by a water scrubber, and the hydrogen yield was 4.4kg/h. And 645kg/h of tower bottom byproduct 30wt% sodium hydroxide alkali liquor is led out to a carbon dioxide alkali washing tower to absorb the carbon dioxide with the concentration of 8-11% in the flue gas from the outlet of the PTA waste water incineration boiler, the temperature is lower than 110 ℃, the pH value of the absorption liquid at the outlet of the absorption tower is controlled to 12 to generate sodium carbonate solution, the sodium carbonate solution is recovered by an evaporation crystallization unit, and the absorbed flue gas is discharged through a chimney.
While embodiments of the present application have been illustrated and described above, it will be appreciated that the above described embodiments are illustrative and should not be construed as limiting the application. The present application is subject to various changes and modifications without departing from the spirit and scope thereof, and such changes and modifications fall within the scope of the application as hereinafter claimed.
Claims (10)
1. The device for preparing bromine and hydrogen by integrating PTA incineration ash and slag through electrolytic rectification is characterized in that: the device comprises an annular electrolytic rectifying tower, wherein the annular electrolytic rectifying tower comprises an electrolytic tower kettle section at the lower part and a rectifying section at the upper part, and the lower part of the rectifying section stretches into the electrolytic tower kettle section; the electrolytic tower kettle section is sequentially provided with a cathode (1), a bipolar membrane (2), a cation exchange membrane (3) and an anion exchange membrane (4) which are concentrically and annularly arranged from outside to inside, wherein an anode (5) is arranged in the anion exchange membrane (4), the bipolar membrane (2), the cation exchange membrane (3), the anion exchange membrane (4) and the bottom of the annular electrolytic rectifying tower are in sealed connection, the bipolar membrane (2) is formed by compositing the cation exchange membrane and the anion exchange membrane, and the cation exchange membrane of the bipolar membrane (2) is arranged at the side close to the cathode (1); the upper part of the cation exchange membrane (3) is connected with the bottom of the side wall of the rectifying section in a sealing way, the upper part of the anion exchange membrane (4) is connected and sealed with the inner wall of the rectifying section through an inclined panel which is used for the liquid of the rectifying section to slide down, a feeding chamber is formed between the cation exchange membrane (3) and the anion exchange membrane (4), a cathode chamber is formed between the cathode (1) and the bipolar membrane (2), an alkali chamber is formed between the bipolar membrane (2) and the cation exchange membrane (3), a cation chamber is formed between the anode (5) and the anion exchange membrane (4), and an empty chamber is formed outside the cation exchange membrane (3) and above the cathode (1) and the bipolar membrane (2).
2. The apparatus for producing bromine and hydrogen by electrolytic rectification of PTA incineration ash as claimed in claim 1, characterized in that: the top of the annular electrolytic rectifying tower is connected with the top of the condensation separator (8), water separated by the condensation separator (8) is returned to the electrolytic rectifying tower, and separated non-condensable gas is returned to the lower part of the rectifying section to maintain the partial pressure of electrolytic oxygen to be more than 10kPa.
3. The apparatus for producing bromine and hydrogen by electrolytic rectification of PTA incineration ash as claimed in claim 1, characterized in that: the annular electrolytic rectifying tower is characterized in that a crystallization separation unit is further arranged in front of the annular electrolytic rectifying tower and comprises a dissolution filtering device, an evaporation crystallization device and a centrifugal separation device which are sequentially connected, and the centrifugal separation device is connected with the annular electrolytic rectifying tower.
4. The apparatus for producing bromine and hydrogen by electrolytic rectification of PTA incineration ash as claimed in claim 1, characterized in that: the operation pressure of the rectifying section is between 20 and 101kPa, the operation temperature of the top plate of the tower is between 50 and 93 ℃, and the reflux ratio is between 0.5 and 5.
5. The apparatus for producing bromine and hydrogen by electrolytic rectification of PTA incineration ash as claimed in claim 3, characterized in that: the alkali chamber of the electrolytic tower kettle section is connected with a flue gas absorption tower, and the absorption liquid of the flue gas absorption tower is sent into an evaporation crystallization device; and delivering the crystals separated by the centrifugal separation device to a drying device, and delivering the mother liquor separated by the centrifugal separation device to a feeding chamber.
6. The method for preparing bromine and hydrogen by integrating PTA incineration ash with electrolytic rectification comprises the steps of sodium carbonate crystallization separation, electrolytic bromine preparation and rectification separation and is characterized in that: the device according to claim 1 is used, after the ash is dissolved and filtered to remove insoluble metal oxide impurities, the filtrate is evaporated and crystallized, 85% -95% of sodium carbonate is crystallized and separated out after evaporation, and after centrifugal separation, the centrifugal mother liquor is sent into a feeding chamber of an electrolytic tower kettle section for electrolysis; a cathode chamber is arranged between the cathode and the bipolar membrane, hydrogen is generated in the cathode chamber, and the hydrogen is sent out after gas-liquid sedimentation separation in the air chamber; an alkali chamber is formed between the bipolar membrane and the cation exchange membrane, wherein NaOH is generated; the sectional area of a positive chamber formed between the anode (5) and the anion exchange membrane (4) is at least 25% of the sectional area of the kettle section of the electrolytic tower, bromine is generated, and the bromine is evaporated in situ after heating and leaves the positive chamber liquid phase.
7. The method for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash as claimed in claim 6, which is characterized in that: the steam leaving the liquid phase of the cation chamber enters a rectifying section, the gas flow which is led out from the top of the rectifying section is led in from the upper part of a condensation separator (8), and the non-condensable gas in the condensation separator (8) is returned to the lower part of the rectifying section to maintain the partial pressure of the electrolytic oxygen to be more than 10kPa.
8. The method for producing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash as claimed in claim 7, which is characterized in that: the condensing separator (8) adopts water cooling, the condensing separator (8) adopts partition wall condensation in a heat exchange mode, the operating pressure of the rectifying section is 20 kPa-101 kPa, the operating temperature of the top of the rectifying section is 50-93 ℃, and the reflux ratio is 0.5-5.
9. The method for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash as claimed in claim 6, which is characterized in that: the ash slag is dissolved to obtain a solution with the mass fraction of 20% -25%, and the filtrate is evaporated and centrifuged to separate sodium carbonate crystals to obtain a centrifugal mother solution; the mass concentration of sodium bromide in the feeding solution fed into the feeding chamber is 20% -50% and the mass concentration of sodium carbonate is 1% -10%.
10. The method for preparing bromine and hydrogen by integrating electrolytic rectification of PTA incineration ash as claimed in claim 6, which is characterized in that: the electrolysis voltage between the cathode and the anode is 1.2V-3V, the temperature of the kettle section of the electrolysis tower is 60-100 ℃, and the partial pressure of the electrolytic oxygen is more than 10kPa.
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| CN116855965B (en) * | 2023-09-04 | 2023-11-14 | 浙江百能科技有限公司 | PTA alkali recovery furnace molten salt separation and purification device |
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