CN109775898A - Phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling technique and its system - Google Patents
Phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling technique and its system Download PDFInfo
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- CN109775898A CN109775898A CN201910217789.9A CN201910217789A CN109775898A CN 109775898 A CN109775898 A CN 109775898A CN 201910217789 A CN201910217789 A CN 201910217789A CN 109775898 A CN109775898 A CN 109775898A
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- triethylamine
- phosphoric acid
- waste liquid
- adjustment
- membrane
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 title claims abstract description 177
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 57
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000007788 liquid Substances 0.000 title claims abstract description 56
- 238000004064 recycling Methods 0.000 title claims abstract description 51
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000004411 aluminium Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 71
- 238000010979 pH adjustment Methods 0.000 claims abstract description 39
- 238000011084 recovery Methods 0.000 claims abstract description 29
- -1 phosphate anion Chemical class 0.000 claims abstract description 28
- 102100031695 DnaJ homolog subfamily C member 2 Human genes 0.000 claims abstract description 22
- 101000845887 Homo sapiens DnaJ homolog subfamily C member 2 Proteins 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 21
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 20
- 239000010452 phosphate Substances 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- 239000012528 membrane Substances 0.000 claims description 62
- 238000001223 reverse osmosis Methods 0.000 claims description 31
- 239000012141 concentrate Substances 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 22
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 150000001412 amines Chemical class 0.000 claims description 15
- 238000001471 micro-filtration Methods 0.000 claims description 10
- 238000001728 nano-filtration Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000012163 sequencing technique Methods 0.000 claims description 3
- 230000007613 environmental effect Effects 0.000 abstract description 6
- 230000036642 wellbeing Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- 239000002585 base Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000000895 extractive distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 1
- 235000019799 monosodium phosphate Nutrition 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling technique and its systems comprising the first pH adjusts system, the 2nd pH adjustment system, the 3rd pH adjustment system, ZRF1 system, ZRF2 system, ZRF3 system, ZRF4 system, ZRF5 system, ZRF6 system, ZRF7 system, chemical phosphorus removal system, triethylamine recovery system and phosphoric acid recovery system；Processing step provided by the invention is reasonable, the highly concentrated waste liquid of phosphoric acid aluminium, triethylamine is concentrated, separates recycling, the phosphate anion in waste liquid phosphoric acid is separated and recovered from simultaneously, triethylamine separates and recovers triethylamine, then water process is reached into reuse after originally water quality standard, resource reclaim in waste liquid is realized while the waste liquid disposition expense substantially reduced to recycle, conducive to environmental protection, water resource is saved, economic well-being of workers and staff is brought.
Description
Technical field
The present invention relates to waste liquid concentration, separation, recovery and reuse technology field, in particular to a kind of phosphoric acid aluminium, three second
Amine high-concentration waste liquid recycling technique and its system.
Background technique
Before new catalysts materials, aluminum material in the industrial processes such as processing, produces and largely contain aluminum phosphate, three
Ethamine high-concentration waste liquid contains a large amount of phosphate anion, organic matter, organic amine, aluminium salt etc., these pollution factors in the waste liquid
Environment water is polluted extremely serious, phosphate anion, organic amine, which are largely discharged into water body, can make water eutrophication and bring pair
The secondary pollution of environment, triethylamine is toxic as surfactant, has strong and stimulating, causes serious pollution to the environment.
Manufacturing enterprise entrusts qualified specialized company to handle for such waste liquid as danger wastes at present, handles work
Skill generally heats the method recycling phosphoric acid of distillation and concentration, and energy consumption is high, and equipment requirement is high, while in distillation process, organic amine volatilization,
COD, ammonia nitrogen concentration are high in its condensed water, aluminium for needing to be removed organic matter and ammonia nitrogen again, while containing in waste liquid etc. from
Son influences phosphoric acid recycling, and entire process operation is at high cost, equipment manufacturing cost is big.Traditional handicraft is generally gone by the way of extractive distillation
Except the triethylamine in waste liquid, but since triethylamine is easy to form stable colloidal substance with the P elements in water, directly adopt
The methods of extractive distillation is difficult to remove the triethylamine in waste water.Meanwhile aluminium ion is rich in waste liquid, such as use chemical precipitation method
When removing aluminium ion, organic amine is decomposed into amino molecule, it is more difficult to removal of ammonia and nitrogen and total nitrogen.
Summary of the invention
In view of the above-mentioned deficiencies, one of the object of the invention is, provide it is a kind of can be to phosphoric acid aluminium, triethylamine high-concentration waste
Liquid carries out recovery processing recycling, and the good phosphoric acid aluminium of utilizing status, triethylamine high-concentration waste liquid recycling technique.
The present invention also aims to provide that a kind of to implement above-mentioned phosphoric acid aluminium, the recycling of triethylamine high-concentration waste liquid sharp again
With the system of technique.
To achieve the above object, provided technical solution is the present invention: a kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid
Recycling technique comprising following steps:
(1) first time pH is adjusted: the high-concentration waste liquid of phosphoric acid aluminium and triethylamine being extracted into the first pH adjustment system and carries out pH tune
It is whole, pH value is adjusted to 5 ~ 6；
(2) ZRF1 system is handled: will pass through the function of ZRF1 system through step (1) treated waste liquid enters ZRF1 system processing
Energy film filtration, removes the most of bulky grain suspended particulate and colloid in waste liquid；
(3) second pH adjustment: will through step (2), treated that water outlet is sent into the 2nd pH adjustment system carries out pH adjustment, adjust
PH value is to pH < 4；
(4) ZRF2 system is handled: the water outlet handled through step (3) enters the processing of ZRF2 system, passes through the functional membrane of ZRF2 system
By the phosphate anion separation in waste liquid, obtains and produce water and concentrate；
(5) ZRF3 system is handled: the production water handled through step (4) enters ZRF3 system, anti-using the functional membrane in ZRF3 system
Phosphate anion is concentrated osmosis；
(6) ZRF4 system is handled: the concentrate handled through step (5) enters the processing of ZRF4 system, utilizes the function of ZRF4 system
Membrane reverse osmosis effect, further concentrated phosphoric acid radical ion；
(7) phosphoric acid recycles: through step (6), treated that high power concentrate enters that phosphoric acid recovery system carries out phosphoric acid recycling；
(5 ') chemical dephosphorization: the concentrate after step (4) separating treatment enters chemical phosphorus removal system, will be remaining a small amount of in waste liquid
Phosphate radical by way of chemical dephosphorization, remove concentrate in phosphate radical；
(6 ') third time pH adjustment: through step (5 ') treated water outlet enter the 3rd pH adjustment system carry out pH adjustment, adjust
PH value is to pH < 4；
The processing of (7 ') ZRF5 system: the water outlet handled through step (6 ') enters the processing of ZRF5 system, utilizes the function of ZRF5 system
Membrane reverse osmosis effect, is concentrated triethylamine；
The processing of (8 ') ZRF6 system: the concentrate after step (7 ') concentration is lifted into the processing of ZRF6 system, utilizes
The functional membrane counter osmosis of ZRF6 system, is further concentrated triethylamine；
The recycling of (9 ') triethylamine: the high power concentrate handled through step (8 ') enters triethylamine recovery system and carries out three second of recycling
Amine；
Finally, through ZRF3 system, ZRF4 system, ZRF5 system and ZRF6 system treated produce water enter at ZRF7 system
Reason makes production water reach reuse after reuse standard, realizes the purpose of recycling and reusing；
Wherein the step (5), (6), (7) and (5 '), (6 '), (7 '), (8 '), (9 ') are without sequencing.
As an improvement of the present invention, further comprising the steps of: the concentrate recirculation of the ZRF7 system to the first pH
Adjustment system.
As an improvement of the present invention, the chemical phosphorus removal system carries out dephosphorization using dephosphorization agent.
As an improvement of the present invention, the ZRF1 system is tube microfiltration membrane system, ZRF2 system is nanofiltration membrane system
System, ZRF3 system are reverse osmosis membrane system with high salt, ZRF4 system is high pressure reverse osmosis membrane system with high salt, ZRF5 system is with high salt anti-
Permeate membranous system, ZRF6 system is high pressure reverse osmosis membrane system with high salt, ZRF7 system is ordinary RO membrane system.
A kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling and reusing system comprising the first pH adjusts system, second
PH adjusts system, the 3rd pH adjusts system, ZRF1 system, ZRF2 system, ZRF3 system, ZRF4 system, ZRF5 system, ZRF6 system
System, ZRF7 system, chemical phosphorus removal system, triethylamine recovery system and phosphoric acid recovery system, the first pH adjust system, ZRF1
System, the 2nd pH adjustment system and ZRF2 system are sequentially connected and connect, the production water end (W.E.) of the ZRF2 system, ZRF3 system, ZRF4 system
System and phosphoric acid recovery system, which are sequentially connected, to be connect；The concentrated water end of the ZRF2 system, chemical phosphorus removal system, the 3rd pH adjustment system,
ZRF5 system, ZRF6 system and triethylamine recovery system are sequentially connected and connect, the ZRF7 system respectively with the ZRF3 system,
ZRF4 system, ZRF5 system are connected with the production water end (W.E.) of ZRF6 system.
As an improvement of the present invention, the concentrated water end of the ZRF7 system is connected with the first pH adjustment system.
As an improvement of the present invention, the ZRF1 system is tube microfiltration membrane system.The ZRF2 system is nanofiltration
Membranous system, ZRF7 system are ordinary RO membrane system.The ZRF3 system is reverse osmosis membrane system with high salt, and ZRF5 system is height
Salt reverse osmosis membrane system.The ZRF4 system is high pressure reverse osmosis membrane system with high salt, ZRF6 system is high pressure reverse osmosis membrane with high salt
System.
The invention has the benefit that processing step provided by the invention is reasonable, first in ZRF1 system removal waste liquid
Most of bulky grain suspended particulate and colloid, then by ZRF2 system by waste liquid phosphate anion separate, utilize ZRF3
System and ZRF4 system are successively concentrated phosphate anion, subsequently enter phosphoric acid recovery system and carry out phosphoric acid recycling；And it passes through
Concentrate after step (4) separating treatment enters the phosphate radical that chemical phosphorus removal system is removed in concentrate, passes through ZRF5 system
System and ZRF6 system are successively concentrated triethylamine, subsequently enter triethylamine recovery system and carry out recycling triethylamine, realization pair
Phosphoric acid aluminium, triethylamine highly concentrated waste liquid be concentrated, separate recycling, while the phosphate anion in waste liquid being separated and being returned
Phosphoric acid, triethylamine separation and recovery triethylamine have been received, reuse after originally water quality standard will be reached after water process finally by ZRF7 system,
While the waste liquid disposition expense substantially reduced, realizes resource reclaim in waste liquid and recycle, be conducive to environmental protection, save water resource, band
Carry out economic well-being of workers and staff.
With reference to the accompanying drawing with embodiment, the present invention is further described.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
Fig. 2 is structural schematic diagram of the invention.
Specific embodiment
Embodiment: referring to Fig. 1 and Fig. 2, the embodiment of the present invention provides a kind of phosphoric acid aluminium, the recycling of triethylamine high-concentration waste liquid
Reutilization system comprising the first pH adjust system 1, the 2nd pH adjustment system 3, the 3rd pH adjustment system 9, ZRF1 system 2,
ZRF2 system 4, ZRF3 system 5, ZRF4 system 6, ZRF5 system 10, ZRF6 system 11, ZRF7 system 13, chemical phosphorus removal system 8,
Triethylamine recovery system 12 and phosphoric acid recovery system 7, the first pH adjustment system 1, ZRF1 system 2, the 2nd pH adjust system 3
It is sequentially connected and connects with ZRF2 system 4, production water end (W.E.), ZRF3 system 5, ZRF4 system 6 and the phosphoric acid recovery system of the ZRF2 system 4
7 are sequentially connected and connect；The concentrated water end of the ZRF2 system 4, chemical phosphorus removal system 8, the 3rd pH adjustment system 9, ZRF5 system 10,
ZRF6 system 11 and triethylamine recovery system 12 are sequentially connected and connect, the ZRF7 system 13 respectively with the ZRF3 system 5, ZRF4
System 6, ZRF5 system 10 are connected with the production water end (W.E.) of ZRF6 system 11.
Preferably, the concentrated water end of the ZRF7 system 13 is connected with the first pH adjustment system 1, realize to ZRF7 system 13
The concentrated water being discharged carries out recovery processing recycling.
In the present embodiment, the ZRF1 system 2 is tube microfiltration membrane system.Tube microfiltration membrane system is by tubular type micro-filtration
The low pressure separating technology that film separates solid from solution.The structure of tube microfiltration membrane includes made of HDPE material sintering
Support frame, the internal structure of support frame are out the multidirectional hole reticular structure of room.It is filled in the hole of these support frames
PVDF filter membrane.Waste water circulating and recovering and object are realized using filtering under lower pressure (0.7-7 bar) by tube microfiltration membrane
Material recycling, the water flow for flowing through film surface can will cut down the particulate matter come and take away, without being gathered in film surface.The tube microfiltration membrane
System directly can reach Environmental Protection Technology Co., Ltd, Guangdong Wei Di Science and Technology Ltd. or Henan work of nature environment section to Guangdong Xinfeng
The enterprises such as skill Co., Ltd buy.
The ZRF2 system 4 is nanofiltration membrane system, the nanofiltration membrane in nanofiltration membrane system be between ultrafiltration and it is reverse osmosis between
A kind of membrane separation technique, molecular cut off in the range of 80-1000, aperture be several nanometers.Nanofiltration membrane is with higher
Ion selectivity, it wants low with respect to high valence ion to the rejection of low price ion to high valence ion rejection with higher
Much.For removal efficiency > 80% of phosphate anion.The nanofiltration membrane system can directly Xiang Sanda membrane environment technical concern have
The fast scientific enterprises such as equipment Co., Ltd and Xiamen Starmem Film Technology Co., Ltd. that rub of limit company, Shanghai buy.
The ZRF3 system 5 and ZRF5 system 10 are reverse osmosis membrane system with high salt, and the reverse osmosis membrane system with high salt is preferred
With U.S. Hydranautics reverse osmosis membrane CPA3-LD, for the composite polyamide reverse osmosis membrane for taking into account equipment with high desalinization and high transmission water,
Low pressure operation operation.Can directly have to permanent big industrial Environmental Protection Technology Co., Ltd, Shenzhen and Quanzhou Hydranautics water treatment facilities
The enterprises such as limit company buy.
The ZRF4 system 6 and ZRF6 system 11 are high pressure reverse osmosis membrane system with high salt, relative to reverse osmosis membrane with high salt
System increases high pressure pump assembly, to promote operating pressure.It is reverse osmosis to can choose Tao Shi reverse osmosis membrane XUS180808, Tao Shi
Film XUS180804 or Tao Shi reverse osmosis membrane XUS180802, it is reverse osmosis using high pressure, it can more promote desalting effect.Can directly to
The enterprises such as Xi'an Ju Fang environmental science and technology Co., Ltd and Beijing Shi Chuankaijie water treatment technology Co., Ltd buy.
The ZRF7 system 13 is ordinary RO membrane system.It can be directly to the limited public affairs of Guangdong benefit people water process science and technology
The enterprises such as department, Ningbo gold the Changjiang river Water Management Equipment Ltd. and Dongguan City Tong Quan Environmental Protection Technology Co., Ltd buy.
A kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling technique comprising following steps:
(1) first time pH is adjusted: the high-concentration waste liquid of phosphoric acid aluminium and triethylamine being extracted into the first pH adjustment system 1, uses soda acid
PH adjustment is carried out, adjusts pH value to 5 ~ 6；
(2) ZRF1 system is handled: will through step (1), treated that waste liquid enters that ZRF1 system 2 is handled, high-concentration waste liquid is in low pressure
It is constantly concentrated and separated under state, by the functional membrane filtration of ZRF1 system 2, the most of bulky grain removed in waste liquid suspends
Particle and colloid etc.；
(3) second pH adjustment: will through step (2), treated that water outlet is sent into the 2nd pH adjustment system 3 carries out pH adjustment, adjust
PH value is to pH < 4；
(4) ZRF2 system is handled: the water outlet handled through step (3) enters ZRF2 system 4 and handles, and passes through the function of ZRF2 system 4
Film separates the phosphate anion in waste liquid, obtains and produces water and concentrate；
(5) ZRF3 system is handled: the production water handled through step (4) enters ZRF3 system 5, utilizes the functional membrane in ZRF3 system 5
Phosphate anion is concentrated counter osmosis, isolates salt solute；
(6) ZRF4 system is handled: the concentrate handled through step (5) enters ZRF4 system 6 and handles, and utilizes the function of ZRF4 system
Membrane reverse osmosis effect, further concentrated phosphoric acid radical ion isolate salt solute；
(7) phosphoric acid recycles: through step (6), treated that high power concentrate enters that phosphoric acid recovery system 7 carries out phosphoric acid recycling；Phosphoric acid
Recovery system 7 includes dioxygen water storage tank and by the sequentially connected spent acid storage tank of pipeline, agitating reaction pond, the first filter press, true
Empty distillation reactor, decoloring reaction kettle, the second filter press and recycling acid storage tank.Wherein, agitating reaction pond is with the anti-of stirring
Ying Chi, vacuum distillation reaction kettle are the conventional acid-resistant reacting kettle with insulation jacket, stirring and vacuum pump etc., and decoloring reaction kettle is
Conventional acid-resistant reacting kettle with stirring and insulation jacket, the first filter press and the second filter press are conventional acidproof plate compression
It machine and can be realized by the same plate and frame filter press.Wherein, dioxygen water storage tank is anti-by pipeline and agitating reaction pond, vacuum distillation
Kettle is answered to connect with decoloring reaction kettle, spent acid storage tank and recycling acid storage tank are connect by pipeline with phosphoric acid production system.Above-mentioned each knot
Pump, flowmeter or valve etc. are set as needed on pipeline between structure.High power concentrate is sent into agitating reaction pond, is passed through double
Oxygen water after stirring period of aeration, is sent into the first filter press and is separated by solid-liquid separation, and filtrate is sent into vacuum distillation reaction kettle and is carried out
Vacuum concentration is accordingly added or is added without as needed hydrogen peroxide in vacuum Concentrating Process, send decoloration anti-after the completion of concentration
Kettle is answered, active carbon and diatomite are added in decoloring reaction kettle, is accordingly added or is added without as needed hydrogen peroxide, decolourized
The second filter press is sent to be separated by solid-liquid separation after, filtrate sends receipts acid storage tank back to, and the phosphoric acid of recycling is sent into phosphoric acid production system and is used for
Production phosphoric acid is sent into by-product production device for producing monosodium phosphate and tertiary sodium phosphate or selling as fire resisting
Material feedstock, metal conditioner etc. realize the purpose of phosphoric acid recycling；
(5 ') chemical dephosphorization: the concentrate after step (4) separating treatment enters chemical phosphorus removal system 8, will be remaining few in waste liquid
The phosphate radical of amount removes the phosphate radical in concentrate by way of chemical dephosphorization；Specifically, the chemical phosphorus removal system 8 is adopted
Dephosphorization is carried out with dephosphorization agent.
(6 ') third time pH adjustment: through step (5 ') treated water outlet enter the 3rd pH adjustment system 9 carry out pH adjustment,
PH value is adjusted to pH < 4；
The processing of (7 ') ZRF5 system: the water outlet handled through step (6 ') enters ZRF5 system 10 and handles, and utilizes ZRF5 system 10
Triethylamine is concentrated in functional membrane counter osmosis；
The processing of (8 ') ZRF6 system: the concentrate after step (7 ') concentration is lifted into the processing of ZRF6 system 11, utilizes
The functional membrane counter osmosis of ZRF6 system 11 removes the organic matter in water removal, triethylamine is further concentrated；
The recycling of (9 ') triethylamine: the high power concentrate handled through step (8 ') enters triethylamine recovery system 12 and carries out three second of recycling
Amine；Triethylamine recovery system 12 includes including recycling kettle, blender, collet, thermometer and layering visor.The recycling bottom portion
Discharge port be sequentially connected outlet valve, threeway, layering visor, shunt valve and waste pipe, the side port of threeway is by dividing amine valve to connect
Recycle amine pipe.The stirring port of the recycling kettle top center is equipped with blender, and the temperature-measuring port at top is inserted with thermometer boss, temperature
Thermometer is inserted in meter casing, the amine salt mouth of a river at top connects amine salt water pipe by amine salt water valve, and the concentrated base mouth at top passes through dense
Alkali valve connects concentrated base pipe, and the drain at top connects blow-down pipe by blow valve.Collet, collet bottom are equipped with outside the recycling kettle
The water inlet in portion connects water inlet pipe by inlet valve, and the water outlet on collet top connects outlet pipe by outlet valve.Open emptying
Valve makes to recycle kettle holding normal pressure state；Inlet valve, outlet valve are opened, 15~30 DEG C of recirculated water is passed through into collet；Open amine
Brine valve introduces the high power concentrate handled through step (8 ') by amine salt water pipe.Introducing finishes, and closes amine salt water valve；Starting
Blender；Concentrated base valve is opened, alkali solution is added by concentrated base pipe, the aperture of concentrated base valve and inlet valve is controlled in the process, makes
The temperature that thermometer is shown maintains 20~30 DEG C, and alkali is added to finish, and closes concentrated base valve.Continue to stir 10min, stops blender, it is quiet
It sets 30min, opens outlet valve, slowly open shunt valve, water layer is released by waste pipe, when there is phase boundary in being layered visor
When face, shunt valve is closed, water layer separation terminates.Opening divides amine valve, and triethylamine is put into container containing by recycling amine pipe, is returned
Receive triethylamine.It receives amine to finish, closing divides amine valve, outlet valve, retains in shunt valve into the pipeline between threeway side port a small amount of
Triethylamine and waste water are temporarily sealed up for safekeeping wherein, give over to and merge layered shaping with next group.
Finally, through ZRF3 system 5, ZRF4 system 6, ZRF5 system 10 and ZRF6 system 11 treated produce water enter ZRF7
System 13 is handled, and so that production water is reached reuse after reuse standard, the purpose of recycling and reusing is realized, so that water resource is filled
Divide and recycles；The concentrate recirculation of the ZRF7 system 13 adjusts system 1 to the first pH, what ZRF7 system 13 was discharged in realization
Concentrated water carries out recovery processing recycling；
Wherein the step (5), (6), (7) and (5 '), (6 '), (7 '), (8 '), (9 ') are without sequencing.
According to the disclosure and teachings of the above specification, those skilled in the art in the invention can also be to above-mentioned embodiment party
Formula is changed and is modified.Therefore, the invention is not limited to the specific embodiments disclosed and described above, to of the invention
Some modifications and changes should also be as falling into the scope of the claims of the present invention.In addition, although being used in this specification
Some specific terms, these terms are merely for convenience of description, does not limit the present invention in any way.Such as the present invention
Described in above-described embodiment, using same or similar treatment process and water treatment system, all fall in the scope of protection of the present invention.
Claims (10)
1. a kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling technique, which is characterized in that itself the following steps are included:
(1) first time pH is adjusted: the high-concentration waste liquid of phosphoric acid aluminium and triethylamine being extracted into the first pH adjustment system and carries out pH tune
It is whole, pH value is adjusted to 5 ~ 6；
(2) ZRF1 system is handled: will pass through the function of ZRF1 system through step (1) treated waste liquid enters ZRF1 system processing
Energy film filtration, removes the most of bulky grain suspended particulate and colloid in waste liquid；
(3) second pH adjustment: will through step (2), treated that water outlet is sent into the 2nd pH adjustment system carries out pH adjustment, adjust
PH value is to pH < 4；
(4) ZRF2 system is handled: the water outlet handled through step (3) enters the processing of ZRF2 system, passes through the functional membrane of ZRF2 system
By the phosphate anion separation in waste liquid, obtains and produce water and concentrate；
(5) ZRF3 system is handled: the production water handled through step (4) enters ZRF3 system, anti-using the functional membrane in ZRF3 system
Phosphate anion is concentrated osmosis；
(6) ZRF4 system is handled: the concentrate handled through step (5) enters the processing of ZRF4 system, utilizes the function of ZRF4 system
Membrane reverse osmosis effect, further concentrated phosphoric acid radical ion；
(7) phosphoric acid recycles: through step (6), treated that high power concentrate enters that phosphoric acid recovery system carries out phosphoric acid recycling；
(5 ') chemical dephosphorization: the concentrate after step (4) separating treatment enters chemical phosphorus removal system, will be remaining a small amount of in waste liquid
Phosphate radical by way of chemical dephosphorization, remove concentrate in phosphate radical；
(6 ') third time pH adjustment: through step (5 ') treated water outlet enter the 3rd pH adjustment system carry out pH adjustment, adjust
PH value is to pH < 4；
The processing of (7 ') ZRF5 system: the water outlet handled through step (6 ') enters the processing of ZRF5 system, utilizes the function of ZRF5 system
Membrane reverse osmosis effect, is concentrated triethylamine；
The processing of (8 ') ZRF6 system: the concentrate after step (7 ') concentration is lifted into the processing of ZRF6 system, utilizes
The functional membrane counter osmosis of ZRF6 system, is further concentrated triethylamine；
The recycling of (9 ') triethylamine: the high power concentrate handled through step (8 ') enters triethylamine recovery system and carries out three second of recycling
Amine；
Finally, through ZRF3 system, ZRF4 system, ZRF5 system and ZRF6 system treated produce water enter at ZRF7 system
Reason makes production water reach reuse after reuse standard, realizes the purpose of recycling and reusing；
Wherein the step (5), (6), (7) and (5 '), (6 '), (7 '), (8 '), (9 ') are without sequencing.
2. phosphoric acid aluminium according to claim 1, triethylamine high-concentration waste liquid recycling technique, which is characterized in that
Its is further comprising the steps of: the concentrate recirculation of the ZRF7 system to the first pH adjusts system.
3. phosphoric acid aluminium according to claim 1, triethylamine high-concentration waste liquid recycling technique, which is characterized in that
The chemical phosphorus removal system carries out dephosphorization using dephosphorization agent.
4. phosphoric acid aluminium according to claim 1, triethylamine high-concentration waste liquid recycling technique, which is characterized in that
The ZRF1 system is tube microfiltration membrane system, ZRF2 system is nanofiltration membrane system, ZRF3 system be reverse osmosis membrane system with high salt,
ZRF4 system is high pressure reverse osmosis membrane system with high salt, ZRF5 system is reverse osmosis membrane system with high salt, ZRF6 system is that high pressure is with high salt
Reverse osmosis membrane system, ZRF7 system are ordinary RO membrane system.
5. a kind of phosphoric acid aluminium, triethylamine high-concentration waste liquid recycling and reusing system, which is characterized in that it includes the first pH adjustment
System, the 2nd pH adjustment system, the 3rd pH adjust system, ZRF1 system, ZRF2 system, ZRF3 system, ZRF4 system, ZRF5 system
System, ZRF6 system, ZRF7 system, chemical phosphorus removal system, triethylamine recovery system and phosphoric acid recovery system, the first pH adjustment
System, ZRF1 system, the 2nd pH adjustment system and ZRF2 system are sequentially connected and connect, the production water end (W.E.) of the ZRF2 system, ZRF3 system
System, ZRF4 system and phosphoric acid recovery system are sequentially connected and connect；The concentrated water end of the ZRF2 system, chemical phosphorus removal system, the 3rd pH
Adjustment system, ZRF5 system, ZRF6 system and triethylamine recovery system are sequentially connected and connect, the ZRF7 system respectively with it is described
ZRF3 system, ZRF4 system, ZRF5 system are connected with the production water end (W.E.) of ZRF6 system.
6. phosphoric acid aluminium according to claim 5, triethylamine high-concentration waste liquid recycling and reusing system, which is characterized in that
The concentrated water end of the ZRF7 system is connected with the first pH adjustment system.
7. phosphoric acid aluminium according to claim 5 or 6, triethylamine high-concentration waste liquid recycling and reusing system, feature exist
In the ZRF1 system is tube microfiltration membrane system.
8. phosphoric acid aluminium according to claim 5 or 6, triethylamine high-concentration waste liquid recycling and reusing system, feature exist
In the ZRF2 system is nanofiltration membrane system, and ZRF7 system is ordinary RO membrane system.
9. phosphoric acid aluminium according to claim 5 or 6, triethylamine high-concentration waste liquid recycling and reusing system, the ZRF3
System is reverse osmosis membrane system with high salt, and ZRF5 system is reverse osmosis membrane system with high salt.
10. phosphoric acid aluminium according to claim 5 or 6, triethylamine high-concentration waste liquid recycling and reusing system, the ZRF4
System is high pressure reverse osmosis membrane system with high salt, ZRF6 system is high pressure reverse osmosis membrane system with high salt.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113041787A (en) * | 2019-12-26 | 2021-06-29 | 国家能源投资集团有限责任公司 | Method and device for recovering diluted amine liquid |
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| GB772178A (en) * | 1953-12-10 | 1957-04-10 | Southern Production Company In | Production of tris(n-dimethyl) phosphoric acid amide |
| CA1090984A (en) * | 1977-04-13 | 1980-12-09 | Albert Y. Fang | Reclamation of phosphate from bright dip drag-out |
| CA2228158A1 (en) * | 1995-08-07 | 1997-02-20 | Zenon Environmental, Inc. | Producing high purity water using reverse osmosis |
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