CN106890572A - Dilute sulfuric acid electrodialysis concentrates film group device - Google Patents
Dilute sulfuric acid electrodialysis concentrates film group device Download PDFInfo
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- CN106890572A CN106890572A CN201510970291.1A CN201510970291A CN106890572A CN 106890572 A CN106890572 A CN 106890572A CN 201510970291 A CN201510970291 A CN 201510970291A CN 106890572 A CN106890572 A CN 106890572A
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- acidproof
- sulfuric acid
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- dilute sulfuric
- electrodialysis
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 64
- 239000012141 concentrate Substances 0.000 title claims abstract description 13
- 239000012528 membrane Substances 0.000 claims abstract description 42
- 239000002253 acid Substances 0.000 claims abstract description 30
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 30
- 239000002131 composite material Substances 0.000 claims abstract description 21
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 10
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 125000003277 amino group Chemical group 0.000 claims abstract description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- 238000005245 sintering Methods 0.000 claims description 17
- 150000002500 ions Chemical class 0.000 claims description 15
- 229910052697 platinum Inorganic materials 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 14
- 238000004132 cross linking Methods 0.000 claims description 14
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 12
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 12
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 11
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 10
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- PVBMXMKIKMJQRK-UHFFFAOYSA-N 1-chloro-4-(4-chlorobutoxy)butane Chemical compound ClCCCCOCCCCCl PVBMXMKIKMJQRK-UHFFFAOYSA-N 0.000 claims description 3
- 240000002853 Nelumbo nucifera Species 0.000 claims description 3
- 235000006508 Nelumbo nucifera Nutrition 0.000 claims description 3
- 230000004913 activation Effects 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000037452 priming Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 18
- 238000005516 engineering process Methods 0.000 abstract description 6
- 239000004743 Polypropylene Substances 0.000 description 16
- 239000013505 freshwater Substances 0.000 description 9
- 230000008676 import Effects 0.000 description 8
- 238000005507 spraying Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 238000010612 desalination reaction Methods 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- 239000003014 ion exchange membrane Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- -1 polypropylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000002562 thickening agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000000502 dialysis Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical compound Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 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
- 241000272534 Struthio camelus Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000012206 bottled water Nutrition 0.000 description 1
- 238000005518 chemical engineering design Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005370 electroosmosis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052602 gypsum Inorganic materials 0.000 description 1
- 239000010440 gypsum Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- WHWSEYQRQYKZGX-UHFFFAOYSA-N iridium platinum tantalum Chemical compound [Ta].[Ir].[Pt] WHWSEYQRQYKZGX-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- LEYNFUIKYCSXFM-UHFFFAOYSA-N platinum tantalum Chemical compound [Ta][Pt][Ta] LEYNFUIKYCSXFM-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/56—Electro-osmotic dewatering
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/44—Ion-selective electrodialysis
- B01D61/46—Apparatus therefor
- B01D61/48—Apparatus therefor having one or more compartments filled with ion-exchange material, e.g. electrodeionisation
- B01D61/485—Specific features relating to the ion-exchange material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/28—Specific concentration chambers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2313/00—Details relating to membrane modules or apparatus
- B01D2313/34—Energy carriers
- B01D2313/345—Electrodes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2317/00—Membrane module arrangements within a plant or an apparatus
- B01D2317/08—Use of membrane modules of different kinds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/42—Ion-exchange membranes
Landscapes
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Urology & Nephrology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention belongs to water-treatment technology field, and in particular to an electrodialysis plant for dilute sulfuric acid concentration；The dilute sulfuric acid electrodialysis concentrates film group device, including acidproof electrode, acidproof composite diaphragm, acidproof anode membrane, resistance acid cavity block.Wherein electrode is that titanium applies tantalum platinoiridita electrode；Dividing plate is composite elastic dividing plate, is made by PP, PTFE；Acidproof anode membrane is grafted anode membrane using perfluor；The sour cavity block of resistance to 0.01~10% dilute sulfuric acid can be concentrated into more than 20% homogeneous membrane electrodialysis film group device using the cavity block of butyl quaternary amine functional group.
Description
Technical field
The invention belongs to water-treatment technology field, and in particular to an electrodialysis plant for dilute sulfuric acid concentration.
Background technology
Sulfuric acid is one of most widely used basic chemical industry product, and sulfuric acid can substantially be divided into three kinds in use
Situation：One is fixed in product as the part of product；Two is to be transformed into undesirable by-product
Product, such as saltcake, gypsum, ferrous sulfate；Three are discharged from product systems in Waste Sulfuric Acid form.Sulfuric acid
A large user be organic chemical industry industry (including crude Treatment industry, printing and dyeing industry etc.), wherein about 1/3
Sulfuric acid be transformed into spent acid；Another sulfuric acid large user is titanium dioxide industry, according to statistics, often produces 1t titanium whites,
By-product is wanted containing 20% or so 7~11t of dilute sulfuric acid；Pickle for metallurgical industry is same.
Waste Sulfuric Acid is diluted and pollutes in use, should not typically be reused in original production system.
These Waste Sulfuric Acids how are processed and reclaim, no matter from the angle for making full use of the natural resources, or from environment
The angle of protection, is all noticeable problem.
So far, the technique of waste acidity recovery is broadly divided into two major classes：One class is acid regeneration；One class is spent acid
Concentration.Because the cost and energy consumption of acid regeneration are all higher, seldom used in actual industrial production.
More in industrial production that sulfuric acid is reclaimed using the method for concentrating waste acid, this kind of method includes that submerged combustion is dense
Contracting, drum-type concentration, vacuum concentration, cooking-pot type concentration and spray concentration etc..It is especially exactly the energy for concentrating that it is common
Consumption is very high, if concentrated using electrodialysis, its concentration energy consumption will be greatly reduced.
Electrodialytic principle be in the presence of DC electric field, ion permeable selective ion exchange membrane and migrate,
So that the process that electrolyte ion is partly separated from solution.
Electrodialytic technique is one of the membrane separation technique developed relatively morning and obtain substantial industrial achievement.The research at initial stage
Can trace back to before twoth century.Most of historic reports, are all French scholar A. from 1748
Noller has found what water energy was started by the experiment that pericystium is diffused into ethanol solution naturally first.This reality
Issue after examination and approval existing and confirm that water energy passes through the phenomenon of osmosis of animal membrane.Graham is found that osmotic phenomena within 1854.
Dubrunfaut has been made first film dialysis device within 1863, has successfully carried out sugar and has been separated with salt.1903
Year Morse and Pierce is respectively placed in two electrodes in solution of the bag filter inside with outside, finds powered
Impurity can more quickly from gel remove.Nineteen twenty-four Pauli is improved using the principle of Chemical Engineering Design
The experimental rig of Morse, tries hard to mitigate polarization, increases mass transfer rate.Although they are using non-selective
Through film, but these ground-breaking work, practical electrodialytic exploitation generates edification effect after being.
Meyer and Strauss proposes the concept of the multi-compartment electrodialysis plant with Practical significance within 1940.It is special
It is not that nineteen fifty Juda and McRae have succeeded in developing the positive and negative amberplex with high selection permeability
After, just establish the practicality basis of electrodialytic technique.
First electrodialysis plant is made up in nineteen fifty-two of Ionics companies of the U.S. in the world, light for bitter
Change, then put into merchandized handling.Subsequent American and Britain manufacture and electrodialysis device desalination bitter,
Potable water and industrial water, and other countries are transported to successively.Japan just notes at the end of the fifties in last century
The exploitation of heavy this technology, research direction essentially consists in seawater concentration salt manufacturing.Due to function admirable unit price from
Sub- selectivity makes Japan concentrate salt manufacturing in electrodialysis seawater through the exquisiteness studied successfully with technology of film
Technical elements are held the lead so far, produce the t of salt 1,600,000 per year at present.After 1970, Japan is also by electricity
Dialysis is used for brackish water desalination.The sea water desalinating unit of day producing drinking water 120t has been built on island out of office within 1974.
Ionics companies of the U.S. are proposed frequently pole-reversing electroosmosis device within 1972, are adjusted per 10-15min polarities of electrode
Change once, improve the operation stability of device.U.S. Ionpure Technology companies are again raw in recent years
Continuous deionization electrodialysis plant is produced, i.e., filling ion-exchange resin or ion in electrodialysis desalting chamber
Exchange fiber, direct continuously high purity water, and resin is without regeneration.Electrodialysis is studied in the world now
Country have the U.S., Japan, the former Soviet Union, Britain, France, Italy, Germany, Canada, Israel,
Holland, the nations of China and India etc..Technically, the U.S. and Japan are leading.Japan produces amberplex per year about
3.5×105m2.After the seventies in last century, former Soviet Union's development also quickly, produces amberplex per year about
2.5×105m2, wherein 85% is heterogeneous ion-exchange membrane.
The research of China's electrodialytic technique is started from 1958.At the beginning of the sixties, with domestic polyvinyl alcohol heterogeneous membrane
The small-sized electrodialysis plant of assembling just puts into sea trial.Nineteen sixty-five, First is mounted with Chengdu-Kunming railway
Brackish water desalination device.Polystyrene heterogeneous ion-exchange membrane puts into production within 1967, is electrodialytic technique
Popularization and application create condition.After the seventies in last century, electrodialytic technique development is very fast, in ion exchange
The man unit elements such as film, dividing plate, electrode and body construction research aspect all innovated, device to
Regularization, Standardization Development, it is rich in terms of the operational management of System Engineering Design and device to be also accumulated from comparing
Rich experience.The electrodialysis waterwheel for daily output primary pure water 6600t having been built up in Shanghai Jinshan petrochemical industry in 1976
Between, the electrodialytic desalination station for daily output fresh water 200t having been built up in Xisha in 1980.China's amberplex
Annual production stabilization 4.0 × 105m2, account for the 1/3 of world's desalination amberplex.
Simultaneous several adjoint processes in electrodialytic process, it is each with the mass transfer characteristic parameter quantitative description of film
The intensity of individual process.The electric osmose dehydration to be formed is migrated in hydrated ion form, different films are more or less the same.By dense
The electrolyte diffusion coefficient and the infiltration coefficient of water that difference causes differ greatly.These adjoint processes reduce concentration
Multiple and current efficiency, and aggravate with the rising of operation electric current density and film both sides concentration difference.With in, it is low
Concentration feed liquid desalination is compared, and concentration is higher to the mass transfer characteristic parameter request of film, and particularly sour concentration is to film
Requirement it is more taller than the requirement that ordinary salt is concentrated, general heterogeneous ion-exchange membrane is difficult to reach requirement.
But these electrodialytic processes have a common ground, that is, electrodialysis film group device is not acidproof to cannot be used for acid
Concentration, or concentration after acid concentration it is very low, it is impossible to carry out industrial applications.
The content of the invention
For above present situation, on the basis of forefathers study, the particular/special requirement of dilute sulfuric acid is concentrated for electrodialysis,
Carried out series of studies with exploitation, by many-sided experimental study, have developed finally with strong alkali-acid resistance,
Leakage and anti-leakage, anticreep electrodialysis acid concentration specific complex dividing plate, fully solve many external in anti-
The interference effect of factor, it is ensured that the accuracy of service data and repeatability；On this basis, according to electrodialysis
The requirement of acid concentration, continues to the sour cavity block of resistance, acidproof anode membrane, acidproof positive electrode, clamping device, heat exchange
Device, runner design, current density, flow velocity are studied and optimized, and finally developing can be to dilute sulfuric acid
Be concentrated into the acid concentration electrodialysis film group device of 20% concentrations above.
The main object of the present invention is that exploitation is a kind of can be carried out being concentrated into more than 20% to 0.01~10% dilute sulfuric acid
Homogeneous membrane electrodialysis film group device；The present invention also aims to provide it is a kind of can carry out it is economical, environmental protection
The operational factor of dilute sulfuric acid electrodialysis concentration.
What the present invention was achieved by following technical proposals：
A kind of dilute sulfuric acid electrodialysis concentrates film group device, including acidproof electrode, acidproof composite diaphragm, acidproof anode membrane,
The sour cavity block of resistance；Described acidproof electrode, acidproof anode membrane, acidproof composite diaphragm, resistance acid cavity block are arranged in order；
Acidproof electrode is that titanium applies tantalum platinoiridita electrode；Acidproof composite diaphragm is by being combined that PP, PTFE are made
Elastic baffle；Acidproof anode membrane is that perfluor is grafted anode membrane；The sour cavity block of resistance is the cavity block using butyl quaternary amine functional group.
Preferably, the titanium in described dilute sulfuric acid electrodialysis concentration film group device applies tantalum platinoiridita electrode includes titanium plate, platinum
Coating and tantalum oxide, yttrium oxide, ruthenium-oxide mixture coating.
Preferably, the preparation method of the acidproof composite diaphragm in described dilute sulfuric acid electrodialysis concentration film group device
For：One-shot forming is sprayed in the environment of plasma chamber medium and high temperature, inertia using PP, PTFE in batches
Fabrication techniques elastic baffle (described PP, PTFE are respectively polypropylene and polytetrafluoroethylene (PTFE))；
Be 120-220 DEG C in temperature, be first sprayed into the shape of dividing plate with PP, then with PTFE through ion activation after,
PTFE is sprayed at being 220~280 DEG C in temperature on newly formed PP dividing plates and is blended；
The electrode of described gas ions use high-frequency capacitive lotus root composite electrode, 30~50MC of vibration frequency, wait from
Oxygen purity used by daughter is that the ratio of 99.1~99.8%, PTFE is 10%~40%.
Preferably, the acidproof anode membrane in described dilute sulfuric acid electrodialysis concentration film group device be with thickness as 0.1~
The pure tetrafluoroethylene of 0.15mm is counterdie, with irradiation grafting after, then the anode membrane being prepared with impregnated with method,
The film resistance of the anode membrane is 2~4 Ω/cm2, the degree of cross linking is 70~90%, and film thickness is 0.1~0.16mm.
Preferably, the resistance acid cavity block in described dilute sulfuric acid electrodialysis concentration film group device be with thickness be 0.1~
The pure tetrafluoroethylene of 0.15mm is counterdie, with irradiation grafting after, then be prepared with chlorobutyl ether impregnated with method
Cavity block, the film resistance of the cavity block is 3~6 Ω/cm2, the degree of cross linking be 70~90%, film thickness be 0.1~
0.16mm。
A kind of titanium applies the preparation method of tantalum platinoiridita electrode, and the preparation method that described titanium applies tantalum platinoiridita electrode is included such as
Lower step：
Step one, the titanium plate with 0.5~2 millimeters thick, through being cleaned by ultrasonic, after hydrofluoric acid clean, then use oxalic acid
After being surface-treated；
Step 2, step one is processed after titanium plate, carry out primary coat with platinum, platinum coating layer thickness is 0.5~2 micro-
Rice；
Step 3, coating will be carried out with tantalum oxide, yttrium oxide, ruthenium-oxide after step 2 platinum priming coat and sintered,
Coating forms electrode surface coatings, the wherein mass ratio of tantalum oxide, yttrium oxide, ruthenium-oxide ten times with sintering altogether
Example is 0.01~10：0.01~5：0.01~3, sintering temperature is 700-1000 DEG C, and each sintering time is 1-5
Hour.
Specifically,
A kind of dilute sulfuric acid electrodialysis concentrates film group device, including acidproof electrode, acidproof composite diaphragm, acidproof anode membrane,
The sour cavity block of resistance.Wherein electrode is that titanium applies tantalum platinoiridita electrode；Dividing plate is composite elastic dividing plate, by PP, PTFE system
Form；Acidproof anode membrane is grafted anode membrane using perfluor；The sour cavity block of resistance uses the cavity block of butyl quaternary amine functional group.
A kind of acidproof electrode described in dilute sulfuric acid electrodialysis concentration film group device, using the titanium plate of 0.5-2 millimeters thicks,
Through being cleaned by ultrasonic, after hydrofluoric acid clean, then after being surface-treated with oxalic acid, primary coat, platinum coating are carried out with platinum
Thickness is 0.5~2 micron.With tantalum oxide, yttrium oxide, ruthenium-oxide coating is carried out after platinum primary coat and sintered, altogether
Ten formation electrode surface coatings of coating and sintering, the wherein mass ratio of tantalum oxide, yttrium oxide, ruthenium-oxide
It is 0.01~10：0.01~5：0.01~3.Sintering temperature is 700~1000 DEG C, and each sintering time is 1~5
Hour.
Acidproof dividing plate described in a kind of dilute sulfuric acid electrodialysis concentration film group device is composite elastic dividing plate, using PP,
PTFE (PP, PTFE are respectively polypropylene and polytetrafluoroethylene (PTFE)) is in batches in plasma chamber medium and high temperature, lazy
Property in the environment of spray one-shaping technique make elastic baffle.It is 120~220 DEG C in temperature, is first sprayed with PP
Paint the shape of dividing plate, then with PTFE through ion activation after, PTFE is sprayed at being 220~280 DEG C in temperature
It is blended on to the PP dividing plates for being formed just now.The electrode of gas ions uses high-frequency capacitive lotus root composite electrode, shakes
30~50MC of dynamic frequency, the oxygen purity used by plasma is that the ratio of 99.1~99.8%, PTFE is
10%~40%；
In electrodialysis concentration process, electrodialytic membranes used with it is most important.Out-phase EDBM is expanded because of concentration difference
The scattered electrolyte diffusion coefficient for causing is 1~2 order of magnitude of homogeneous membrane, the infiltration coefficient of water is 1 quantity
Level, transference number of ions is also low, constitutes one of principal element of influence concentration concentration.Equally it is homogeneous membrane,
Because the resistance to acid concentration of common anode membrane is limited, when general acid concentration is more than 10%, it is easy to damage.And due to hydrogen from
Sub-volume is especially small, and common cavity block cannot stop, therefore when being concentrated with common homogeneous membrane, when acid concentration is super
When 10%, cavity block declines to a great extent to hydrionic selectivity, so that current efficiency declines to a great extent.In this hair
In bright, we have developed low concentration difference diffusion system, the homogeneous membrane of low water permeability coefficient, resisting high-concentration acid.
Film group device described in a kind of dilute sulfuric acid electrodialysis concentration film group device includes acidproof anode membrane, resistance acid cavity block, wherein
Anode membrane be with pure tetrafluoroethylene that thickness is 0.1~0.15 millimeter as counterdie, with irradiation grafting after, then with containing
The anode membrane that leaching method is prepared, it is 2~4 Ω/cm to control film resistance2, the degree of cross linking is 70~90%, and film thickness is
0.1~0.16mm.It with the pure tetrafluoroethylene that thickness is 0.1~0.15 millimeter is counterdie that the sour cavity block of resistance is also, and is used
After irradiation grafting, then the cavity block being prepared with impregnated with method, but replace the chloromethane of common cavity block with chlorobutyl ether
Ether hinders sour cavity block to prepare, and it is 3~6 Ω/cm to control film resistance2, the degree of cross linking is 70~90%, and film thickness is
0.1~0.16mm.Using these high performance homogeneous ion-exchange membranes, greatly improve the concentration of concentrated vitriol,
And little power consumption, speed are fast.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment
Or the accompanying drawing to be used needed for description of the prior art is briefly described, it should be apparent that, in describing below
Accompanying drawing be only some embodiments of the present invention, for those of ordinary skill in the art, do not paying
On the premise of creative labor, other accompanying drawings can also be obtained according to these accompanying drawings.
Fig. 1 is that dilute sulfuric acid of the invention concentrates electrodialysis film group device structure front schematic view.
Fig. 2 is that dilute sulfuric acid of the invention concentrates electrodialysis film group device texture edge schematic diagram.
Label declaration：1st, anolyte import；2nd, homogeneous acidproof anode membrane；3rd, elastic acidproof dividing plate；4th, it is homogeneous
The sour cavity block of resistance；5th, catholyte import；6th, fastening bolt；7th, diluted acid import；8th, pole liquid runner plate；9、
Anode terminal；10th, steel plate is clamped；11st, light liquid outlet；12nd, concentrated acid outlet；13rd, cathode terminal；
14th, concentrated acid import；15th, platinum tantalum iridium electrode；16th, anolyte outlet；17th, catholyte outlet.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, and following examples are to solution of the invention
Release and the invention is not limited in following examples.
Embodiment 1
The theory structure according to Fig. 1, Fig. 2, installs an electrodialysis thin sulfuric acid thickener, the dilute sulfuric acid
Concentration electrodialysis film group device structure includes anolyte import 1；Homogeneous acidproof anode membrane 2；The acidproof dividing plate 3 of elasticity；
Equal phase resistance acid cavity block 4；Catholyte import 5；Fastening bolt 6；Diluted acid import 7；Pole liquid runner plate 8；Anode
Binding post 9；Clamp steel plate 10；Light liquid outlet 11；Concentrated acid outlet 12；Cathode terminal 13；Concentrated acid import
14；Platinum tantalum iridium electrode 15；Anolyte outlet 16；Catholyte outlet 17；Film group device size uses 400*800mm,
Film group device includes acidproof electrode, acidproof composite diaphragm, acidproof anode membrane, resistance acid cavity block.Wherein acidproof electrode platinum
Primary coat thickness is 1 micron, and tantalum oxide, yttrium oxide, the mass ratio of ruthenium-oxide are 2：3：5；Sintering temperature
It it is 800 DEG C, each sintering time is 4 hours.The PP spraying temperatures for making dividing plate are 160 DEG C, PTFE's
Spraying temperature is 230 DEG C, gas ions electrode vibration frequency 40MC, and the oxygen purity used by plasma is
The ratio of 99.5%, PTFE is 20%；The film resistance of acidproof anode membrane is 3 Ω/cm2, the degree of cross linking is 80%, thickness
It is 0.12mm to spend.The film resistance of the sour cavity block of resistance is 4 Ω/cm2, the degree of cross linking is 85%, and film thickness is 0.13mm.
Enter the light room of electrodialysis by water inlet of the dilute sulfuric acid containing 2% sulfuric acid.Electrodialysis current density is 600A/m2,
Crossflow velocity is 8m/s, and electrodialysis operation water temperature is 36 DEG C.After electrodialysis concentration operation, the fresh water of light room
Concentration is that 0.05% sulfuric acid fresh water can neutralize discharge, and the sulfuric acid concentration of dense room is 20%.At whole dilute sulfuric acid
Reason current efficiency is up to 85%, and total energy consumption is 3 degree of electricity/ton dilute sulfuric acids, significantly less than multiple-effect evaporation.
Embodiment 2
The theory structure according to Fig. 1, Fig. 2, installs an electrodialysis thin sulfuric acid thickener, same to embodiment
1；Film group device size uses 400*800mm, and film group device includes acidproof electrode, acidproof composite diaphragm, acidproof sun
Film, the sour cavity block of resistance.Wherein acidproof electrode platinum primary coat thickness is 1.5 microns, tantalum oxide, yttrium oxide, oxidation
The mass ratio of ruthenium is 3：2：4；Sintering temperature is 850 DEG C, and each sintering time is 4.5 hours.Make
The PP spraying temperatures of dividing plate are 140 DEG C, and the spraying temperature of PTFE is 220 DEG C, gas ions electrode vibration frequency
30MC, the oxygen purity used by plasma is that the ratio of 99.5%, PTFE is 30%；The film electricity of acidproof anode membrane
It is 3.5 Ω/cm to hinder2, the degree of cross linking is 85%, and film thickness is 0.12mm.The film resistance of the sour cavity block of resistance is 4 Ω/cm2,
The degree of cross linking is 80%, and film thickness is 0.12mm.
Enter the light room of electrodialysis by water inlet of the dilute sulfuric acid containing 1.5% sulfuric acid.Electrodialysis current density is 500
A/m2, crossflow velocity is 6m/s, and electrodialysis operation water temperature is 32 DEG C.After electrodialysis concentration operation, light room
Fresh water concentration be that 0.02% sulfuric acid fresh water can neutralize discharge, the sulfuric acid concentration of dense room is 20%.It is whole dilute
Sulfuric acid treatment current efficiency is up to 85%, and total energy consumption is 2.5 degree of electricity/ton dilute sulfuric acids, significantly less than multiple-effect evaporation.
Embodiment 3
The theory structure according to Fig. 1, Fig. 2, installs an electrodialysis thin sulfuric acid thickener, same to embodiment
1；Film group device size uses 600*1200mm, and film group device includes acidproof electrode, acidproof composite diaphragm, acidproof sun
Film, the sour cavity block of resistance.Wherein acidproof electrode platinum primary coat thickness is 1.5 microns, tantalum oxide, yttrium oxide, oxidation
The mass ratio of ruthenium is 3：5：3；Sintering temperature is 850 DEG C, and each sintering time is 3.5 hours.Make
The PP spraying temperatures of dividing plate are 120 DEG C, and the spraying temperature of PTFE is 240 DEG C, gas ions electrode vibration frequency
50MC, the oxygen purity used by plasma is that the ratio of 99.5%, PTFE is 30%；The film electricity of acidproof anode membrane
It is 3.5 Ω/cm to hinder2, the degree of cross linking is 85%, and film thickness is 0.12mm.The film resistance of the sour cavity block of resistance is 4.5 Ω
/cm2, the degree of cross linking is 86%, and film thickness is 0.11mm.
Enter the light room of electrodialysis by water inlet of the dilute sulfuric acid containing 2.5% sulfuric acid.Electrodialysis current density is 1000
A/m2, crossflow velocity is 6m/s, and electrodialysis operation water temperature is 30 DEG C.After electrodialysis concentration operation, light room
Fresh water concentration be that 0.05% sulfuric acid fresh water can neutralize discharge, the sulfuric acid concentration of dense room is 25%.It is whole dilute
Sulfuric acid treatment current efficiency is up to 82%, and total energy consumption is 3.8 degree of electricity/ton dilute sulfuric acids, significantly less than multiple-effect evaporation.
Embodiment 4
The theory structure according to Fig. 1, Fig. 2, installs an electrodialysis thin sulfuric acid thickener, same to embodiment
1；Film group device size uses 600*1200mm, and film group device includes acidproof electrode, acidproof composite diaphragm, acidproof sun
Film, the sour cavity block of resistance.Wherein acidproof electrode platinum primary coat thickness is 2 microns, tantalum oxide, yttrium oxide, ruthenium-oxide
Mass ratio be 3：1：4；Sintering temperature is 900 DEG C, and each sintering time is 3 hours.Make dividing plate
PP spraying temperatures be 150 DEG C, the spraying temperature of PTFE is 250 DEG C, gas ions electrode vibration frequency 50MC,
Oxygen purity used by plasma is that the ratio of 99.5%, PTFE is 25%；The film resistance of acidproof anode membrane is 4
Ω/cm2, the degree of cross linking is 85%, and film thickness is 0.13mm.The film resistance of the sour cavity block of resistance is 5 Ω/cm2, crosslinking
It is 85% to spend, and film thickness is 0.12mm.
Enter the light room of electrodialysis by water inlet of the dilute sulfuric acid containing 3% sulfuric acid.Electrodialysis current density is 900A/m2,
Crossflow velocity is 6m/s, and electrodialysis operation water temperature is 35 DEG C.After electrodialysis concentration operation, the fresh water of light room
Concentration is that 0.05% sulfuric acid fresh water can neutralize discharge, and the sulfuric acid concentration of dense room is 25%.At whole dilute sulfuric acid
Reason current efficiency is up to 85%, and total energy consumption is 4 degree of electricity/ton dilute sulfuric acids, significantly less than multiple-effect evaporation.
Furthermore, it is necessary to illustrate, the specific embodiment described in this specification, the shape of its parts and components,
Named title etc. can be with difference.What all constructions according to described in inventional idea of the present invention, feature and principle were done etc.
Effect or simple change, are included in the protection domain of patent of the present invention.The skill of the technical field of the invention
Art personnel can make various modifications or supplement to described specific embodiment or use similar mode
Substitute, without departing from structure of the invention or surmount scope defined in the claims, all should belong to
In protection scope of the present invention.
Claims (7)
1. a kind of dilute sulfuric acid electrodialysis concentrates film group device, it is characterised in that：Described dilute sulfuric acid electrodialysis concentration
Film group device includes acidproof electrode, acidproof composite diaphragm, acidproof anode membrane, resistance acid cavity block；
Described acidproof electrode, acidproof anode membrane, acidproof composite diaphragm, resistance acid cavity block are arranged in order；
Described acidproof electrode is that titanium applies tantalum platinoiridita electrode；
Described acidproof composite diaphragm is the composite elastic dividing plate being made by PP, PTFE；
Described acidproof anode membrane is that perfluor is grafted anode membrane；
The sour cavity block of described resistance is the cavity block using butyl quaternary amine functional group.
2. dilute sulfuric acid electrodialysis according to claim 1 concentrates film group device, it is characterised in that：Described
Titanium applies tantalum platinoiridita electrode includes titanium plate, platinum coating and tantalum oxide, yttrium oxide, ruthenium-oxide mixture coating.
3. dilute sulfuric acid electrodialysis according to claim 1 concentrates film group device, it is characterised in that：Described
The preparation method of acidproof composite diaphragm is：
One-shot forming skill is sprayed in the environment of plasma chamber medium and high temperature, inertia using PP, PTFE in batches
Art makes elastic baffle；
Be 120-220 DEG C in temperature, be first sprayed into the shape of dividing plate with PP, then with PTFE through ion activation after,
PTFE is sprayed at being 220~280 DEG C in temperature on newly formed PP dividing plates and is blended；
The electrode of described gas ions use high-frequency capacitive lotus root composite electrode, 30~50MC of vibration frequency, wait from
Oxygen purity used by daughter is that the ratio of 99.1~99.8%, PTFE is 10%~40%.
4. dilute sulfuric acid electrodialysis according to claim 1 concentrates film group device, it is characterised in that：Described
Acidproof anode membrane be with pure tetrafluoroethylene that thickness is 0.1~0.15mm as counterdie, with irradiation grafting after, then
The anode membrane being prepared with impregnated with method, the film resistance of the anode membrane is 2~4 Ω/cm2, the degree of cross linking is 70~90%,
Film thickness is 0.1~0.16mm.
5. dilute sulfuric acid electrodialysis according to claim 1 concentrates film group device, it is characterised in that：Described
It with the pure tetrafluoroethylene that thickness is 0.1~0.15mm is counterdie that the sour cavity block of resistance is, with irradiation grafting after, then
The cavity block being prepared with chlorobutyl ether impregnated with method, the film resistance of the cavity block is 3~6 Ω/cm2, the degree of cross linking
It is 70~90%, film thickness is 0.1~0.16mm.
6. film group device is concentrated according to any described dilute sulfuric acid electrodialysis of claim 1 to 5, it is characterised in that：
The dilute sulfuric acid of described dilute sulfuric acid electrodialysis concentration film group device treatment is dilute sulphur that mass fraction is 0.01~10%
Acid.
7. a kind of titanium applies the preparation method of tantalum platinoiridita electrode, it is characterised in that described titanium applies tantalum platinoiridita electrode
Preparation method comprises the following steps：
Step one, the titanium plate with 0.5~2 millimeters thick, through being cleaned by ultrasonic, after hydrofluoric acid clean, then use oxalic acid
After being surface-treated；
Step 2, step one is processed after titanium plate, carry out primary coat with platinum, platinum coating layer thickness is 0.5~2 micro-
Rice；
Step 3, coating will be carried out with tantalum oxide, yttrium oxide, ruthenium-oxide after step 2 platinum priming coat and sintered,
Coating forms electrode surface coatings, the wherein mass ratio of tantalum oxide, yttrium oxide, ruthenium-oxide ten times with sintering altogether
Example is 0.01~10：0.01~5：0.01~3, sintering temperature is 700-1000 DEG C, and each sintering time is 1-5
Hour.
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| CN108097047A (en) * | 2017-12-14 | 2018-06-01 | 杭州水处理技术研究开发中心有限公司 | A kind of dilute sodium hydroxide electrodialysis concentrates film group device |
| CN112456697A (en) * | 2020-12-08 | 2021-03-09 | 杭州水处理技术研究开发中心有限公司 | Forward osmosis acid recovery system |
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| EP0517228A1 (en) * | 1991-06-07 | 1992-12-09 | Asahi Glass Company Ltd. | Method for separating and recovering an acid |
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