CN1611451A - Method for biochemical treatment of discharged water - Google Patents
Method for biochemical treatment of discharged water Download PDFInfo
- Publication number
- CN1611451A CN1611451A CNA2003101049888A CN200310104988A CN1611451A CN 1611451 A CN1611451 A CN 1611451A CN A2003101049888 A CNA2003101049888 A CN A2003101049888A CN 200310104988 A CN200310104988 A CN 200310104988A CN 1611451 A CN1611451 A CN 1611451A
- Authority
- CN
- China
- Prior art keywords
- ion
- water
- acid
- exchange column
- regenerated liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000007788 liquid Substances 0.000 claims abstract description 51
- 238000005342 ion exchange Methods 0.000 claims abstract description 36
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 28
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 claims abstract description 25
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 23
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 21
- 239000002808 molecular sieve Substances 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 16
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 14
- 238000001179 sorption measurement Methods 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 5
- 239000011707 mineral Substances 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 230000001172 regenerating effect Effects 0.000 claims abstract description 5
- 239000003463 adsorbent Substances 0.000 claims description 24
- 230000008929 regeneration Effects 0.000 claims description 23
- 238000011069 regeneration method Methods 0.000 claims description 23
- 150000002500 ions Chemical class 0.000 claims description 15
- 238000010521 absorption reaction Methods 0.000 claims description 13
- 235000017550 sodium carbonate Nutrition 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 235000010755 mineral Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- 229940095064 tartrate Drugs 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 abstract description 16
- 239000000498 cooling water Substances 0.000 abstract description 10
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 4
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000009877 rendering Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 19
- 239000002594 sorbent Substances 0.000 description 15
- 229910021536 Zeolite Inorganic materials 0.000 description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 12
- 239000010457 zeolite Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910021529 ammonia Inorganic materials 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 6
- 239000011575 calcium Substances 0.000 description 6
- 229910052791 calcium Inorganic materials 0.000 description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000003134 recirculating effect Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 241000282326 Felis catus Species 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical group [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 230000000274 adsorptive effect Effects 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001603 clinoptilolite Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 238000009372 pisciculture Methods 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
Abstract
The invention relates to a kind of method for removing ammonia nitrogen, calcium ion and magnesium ion, and meanwhile making wastewater recovered, especially a treatment process of rendering biochemical treating water outlet. The invention uses many ion-exchange columns, and among them, parts take adsorbing and purifying operation, other parts take regenerating operation. Ion-exchanger takes NaY molecular sieve as main material, and after mixing evenly with aluminum hydroxide dry-colloidal powder, filler particle, organic acid, and mineral acid, it can be acquired through forming and roasting. Compared with the ordinary NaY molecular sieve, adsorption capacity of the absorbent manufactured with method of the invention to ammonium ion can be improved greatly, and meanwhile it can detach calcium ion and magnesium ion in the treated water, and outlet water can be used as make-up water to circulating and cooling water. Ion-exchanger uses sodium carbonate solution to regenerate, and then make regenerated liquid have stripping treatment. The wastewater treated with the method of the invention can be used in circulating and cooling water system.
Description
Technical field
The present invention relates to a kind of treatment process of biochemical treatment water outlet, especially refinery contains the deep treatment method of ammonia nitrogen biochemical treatment water outlet.Present method can also be removed calcium ion in the waste water, magnesium ion etc. simultaneously in removal of ammonia and nitrogen, the waste water after the processing be can be used as in the make up water of circulating water system.
Background technology
The service water reuse is to reduce the important channel of polluting, saving water resources, increase economic benefit, and is particularly all the more so for the bigger oil refining enterprise of water resources consumption amount.For oil refining enterprise, the make up water of recirculating cooling water system accounts for 30%～40% of fresh water consumption.The requirement of recirculated cooling water make up water ammonia nitrogen and calcium ion, magnesium ion etc. is comparatively strict.Though the biochemical treatment water outlet conforms to emission standard, the make up water that is used for recirculated water still needs further purifying treatment.
In the present refinery water reclaiming system, mainly contain ozonation technology, photocatalytic-oxidation metallization processes, active carbon absorption technology, reverse osmosis and ultrafiltration technology etc., the organism that reduces in the waste water reduces the tendency that biological sludge produces to reach.But the effect of these technologies is all not very good.
In the removal technology of low-concentration ammonia-nitrogen, be that the ion exchange process of sorbent material has efficiently, the characteristics of low consumption with the zeolite, be widely adopted at present.The ZC-1 type zeolite treatment containing wastewater from catalyst that Qiu's electricity cloud etc. are handled with modification " processing of ammonia nitrogen in the containing wastewater from catalyst " (" mining metallurgical engineering " rolled up the 47th～55 page of the 1st phase in 1994 14), as desorbed solution, its zeolite is 6～9mgNH to the ammonia nitrogen absorption amount with sodium-chlor
4 +-N/g.Han Huiru in " the right zeolite of Anhui Nan Tian to water in the research of ammonia nitrogen absorption performance " (18 the 4th phases of volume of " Jilin Institute of Chemical Technology journal " calendar year 2001), adopts using natural clinoptilolite etc. to adsorb NH in the waste water at " utilizing natural zeolite to handle the technical study of ammoniated wastewater " (" Treatment of Industrial Water " 1997 17 the 5th phases of volume) and Liu Yulin etc.
4 +-N, its zeolite is to NH
4 +-N adsorptive capacity is 11～12mgNH
4 +-N/g zeolite, and the latter points out that this zeolite is not suitable for the wastewater treatment of calcic and magnesium ion.Xiao Tiancun etc. are in " being used for removing the research of the NaA-1 type ion-exchanger of water ammonia nitrogen " (" chemical industry environmental protection " 1997 17 the 6th phases of volume), to be used for ethene exsiccant discarded A molecular sieve trichloromethane, sodium hydroxide and sodium-chlor modification, be used for fertilizer plant's nitrogen-containing wastewater, adsorptive capacity reaches 32mgNH
4 +-N/g, but also point out to be applicable to the wastewater treatment that contains potassium ion and calcium ion.Sodium hydroxide and sodium chloride solution are all adopted in the regeneration of above-mentioned zeolite adsorbents, and cost is higher.CN86106921A is a main raw material with using natural clinoptilolite or mordenite, adding a certain amount of aluminium hydroxide, Repone K, sodium hydroxide and water mixes, carry out complexity then and become steps such as glue, crystallization for a long time, synthetic a kind of sorbent material, the potassium ion or the ammonium ion that can be used for planar water, its preparation process are comparatively complicated.US4,522,727 disclose a kind of L type synthetic zeolite and T type zeolite treatment pisciculture wastewater treatment method used, and have reduced the concentration of non-ionic ammonia in the fishpond, to NH
4 +The adsorption effect of-N is not obvious.US4,717,483 based on activated alumina, cooperates y-type zeolite to make a kind of sorbent material, and molecules of ammonia, sulfide and organism in the absorption leather-making waste water are not considered NH
4 +The influence of-N adsorption effect.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of NH in the biochemical treatment water outlet that removes simultaneously
4 +-N, calcium ion, magnesium ion are the method for recirculating cooling water system make up water with biochemical treatment water outlet purifying treatment.
Studies show that, with the biochemical treatment water outlet during as the cooling water recirculation system make up water, in the forming process of biological clay, the ammonia nitrogen role will be considerably beyond the COD role, in addition, because recirculated cooling water is in the enrichment stage, so the calcium in the make up water, magnesium, the isoionic fouling tendency of iron are very important.At These characteristics, the present invention proposes the purifying treatment method of following a kind of biochemical treatment water outlet.
The deep purifying treatment process of biochemical treatment water outlet of the present invention may further comprise the steps: any placed in-line 1～9 of entering in 2～10 ion exchange columns of biochemical treatment water outlet carries out ion-exchange absorption, and other ion exchange column carries out regenerative operation; The exchange column that reaches capacity in the ion exchange column of series connection absorption switches by its terminal valve and adsorption system, and the ion exchange column after the regeneration switches into adsorption system by its terminal valve.Behind the regenerated liquid disgorging, enter the steam stripped system and regenerate.
The ion adsorbent that uses in the wherein said ion exchange column adopts following method preparation:
(1) is main raw material with the NaY molecular sieve, mixes that the blended weight ratio is 60～80%: 1～20%: 1～10%: 1～10%: 1～10% with aluminium hydrate powder, extrusion aid, organic acid and mineral acid.
(2) moulding.Make diameter 0.5～2mm by banded extruder, length is the fine strip shape of 1～5cm.
(3) roasting.Under 300 ℃～500 ℃ temperature, roasting 4～10 hours.
Wherein the NaY molecular sieve is natural NaY molecular sieve, and the Si/Al atomic ratio is generally 2～5.Aluminium hydrate powder is the aluminium hydrate powder of preparation such as aluminium chloride process, Tai-Ace S 150 method, carbon dioxide process, and in the SB powder one or more.Extrusion aid is generally the blue or green powder in field etc., and organic acid is one or more in formic acid, acetate, propionic acid, toxilic acid, citric acid, tartrate, pentanedioic acid, the hexanodioic acid etc., and mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid etc.
In the regenerative process of ion adsorbent of the present invention, the regenerated liquid of employing is that concentration is 1～20% sodium carbonate solution, and the pH value is 11～14.Regenerated liquid enters ion exchange column from the bottom, and the ammonium ion that adsorbs on the ion adsorbent is replaced with sodium ion, and calcium ion, magnesium ion are converted into throw out.
In adsorbent reactivation process of the present invention, regenerated liquid enters the steam stripped unit behind disgorging.Throw out is concentrated by the method for centrifuge dehydration, adds then and buries processing.The main equipment of steam stripped system is a stripping tower, and regenerated liquid is heated stripping in stripping tower, and the ammonia nitrogen in the regenerated liquid steams from cat head, and the cooling back forms the industrial ammonia of 5%～10% (wt%).Regenerated liquid after the regeneration can reuse after replenishing fresh sodium carbonate solution.
The inventive method can effectively be removed ammonia nitrogen in the biochemical treatment water outlet and calcium, magnesium, iron plasma, ammonia-N removal rate can reach more than 90% (wt%), simultaneously to the clearance of calcium ion, magnesium ion and iron ion greater than 95%, when purifying waste water after the processing is used for the make up water of recirculating cooling water system, suppressed the cooling aquatic system effectively and produced the problem of thing foundry loam and fouling.The inventive method can operate continuously, and regenerated liquid adopts cheap sodium carbonate solution, and running cost is low.Ion exchange absorbent is than the NH of undressed natural NaY molecular sieve
4 +-N loading capacity improves greatly, generally speaking, and the NH of untreated natural NaY molecular sieve
4 +-N loading capacity is about 5.0mg/g, after process the method for the invention is made new adsorbent, and the NH of sorbent material
4 +-N loading capacity improves greatly, can reach more than the 30mg/g, also have absorption calcium, magnesium, the isoionic ability of iron simultaneously, the biochemical treatment water outlet is removed simultaneously to the disadvantageous ammonia nitrogen of recirculated cooling water, calcium ion, magnesium ion and iron ion, regenerability is good, simplify technical process, reduced facility investment and process cost.
Description of drawings
Fig. 1 is the process flow diagram of the inventive method.1, back with water inlet line 2, regenerated liquid pipeline 3, ion exchange column 4, ion exchange column 5 rich ammonium regenerated liquid pipelines 6, stripping tower unit 7, take off ammonium regenerated liquid reuse pipeline 8, ammoniacal liquor gathering line 9, sediment outfall pipeline 10, water outlet pipeline 11, rinse water washing pipeline 12, rinse water outfall pipeline
Embodiment
Further specify the process and the effect of the inventive method below in conjunction with accompanying drawing.(NM valve is and closes)
In Fig. 1, the biochemical treatment water outlet from Sewage Plant at first enters in ion exchange column 3 or 4 by pipeline 1.Ion exchange column 3,4 blocked operations wherein during 1 adsorption operations, are regenerated for other 1.With ion exchange column 3 absorption, meanwhile ion exchange column 4 is regenerated as this flow process of example narration below.
At first valve 3-3,3-4 open, and former water enters exchange column 3, and the sorbent material that is equipped with in the exchange column can adsorb the ammonium ion in the former water, thereby remove the ammonia nitrogen in the former water.Calcium ion, the magnesium ion in the waste water removed in absorption simultaneously.Water outlet is from pipeline 10 discharge systems, and as the make up water of recirculating cooling water system, wherein 5%～10% (wt%) removes to clean ion exchange column 4 as rinse water, and rinse water is walked pipeline 11 flushing ion exchange columns 4 after regenerated liquid has been regenerated ion exchange column 4.
The regenerated liquid that meanwhile contains yellow soda ash enters in the ion exchange column 4 through pipeline 2, ammonium ion that adsorbs on the sorbent material and calcium ion, magnesium ion are under the promotion of concentration difference, be reproduced the sodium ion displacement in the liquid, enter regenerated liquid, the adsorbents adsorb capacity is restored, regenerated liquid becomes rich ammonia regeneration liquid, calcium ion, magnesium ion then with regenerated liquid in carbanion form lime carbonate, magnesiumcarbonate precipitation, these throw outs will in time be removed with purifying regeneration liquid and prevent the blocking pipeline system, and sediment can consider to do landfill disposal as solid waste.Sodium ion in the regenerated liquid then enters on the sorbent material skeleton, becomes tradable positively charged ion on the sorbent material, has played the effect of reproducing adsorbent.Remove the regenerated liquid of post precipitation and send into stripping tower 6 through pipeline 5.Ammonia in stripping tower in the regenerated liquid is entered gas phase by stripping, through condensation, becomes strong aqua at cat head.The heating thermal source of stripping tower is 0.3MPa～1.0MPa steam, and the steam condensate after the heating is got back to condensate system.Regenerated liquid behind the deamination is sent back to through pipeline 7 and to be recycled after cooling.After ion exchange column 4 regeneration, valve 4-1,4-2 open, and wash with rinse water, so that remove the regenerated liquid that adheres on the ion adsorbent, water outlet is directly discharged by pipeline 12.
Waste water in the pipeline 1 contains the ammonia nitrogen of 10～100mg/L usually, the calcium ion of 20～100mg/L, the magnesium ion of 20～80mg/L, after present method processing, in pipeline 10 water outlets, ammonia nitrogen can be reduced to 0～5mg/L, and calcium ion and magnesium ion can be reduced to 0～5mg/L.PH value in the water outlet slightly raises, and former water pH value is about 7.0, and water outlet pH value is between 7.5～8.5.
Regenerated liquid is prepared by 1%～20% concentration by yellow soda ash, pH11～14 can guarantee to have in the regenerated liquid concentration of ammonia nitrogen that more non-ionic ammonia form exists and less ion ammonium, keeping has higher ammonium concentration difference and partial potential between sorbent material and the regenerated liquid, be beneficial to carrying out smoothly of regenerative process.
The regenerated regenerated liquid of exchange column, ammonia-nitrogen content enter stripping tower 6 and carry out stripping and handle between 1000～5000mg/L.Through the regenerated liquid of stripping tower 6, a part becomes gas phase, becomes 5%～10% industrial ammonia through cooling from pipeline 8.The working pressure of stripping tower is 0.01～0.1MPa, 90 ℃～100 ℃ of tower top temperatures, 95 ℃～100 ℃ of column bottom temperatures.In the regenerated liquid behind the stripping, ammonia nitrogen concentration is 0.The heating thermal source of stripping tower 6 is 0.3～1.0MPa steam, and the regenerated liquid heat-eliminating medium behind the stripping is a cooling circulating water.
When ion exchange column 3 and ion exchange column 4 were handled, the air speed of waste water was at 1.0h
-1～5.0h
-1In the regeneration stage, the air speed of regenerated liquid reduces as far as possible, to keep the higher residence time, gets 0.1h usually
-1～0.5h
-1Washing after the regeneration needs higher air speed usually, to guarantee that bed can expand fully, what be beneficial to regenerated liquid and sorbent material separates the common 0.01m/s～0.05m/s of the flow velocity of rinse water, can guarantee the bed expansion rate 20%～40%, the consumption of wash-down water accounts for handles 5～10% of the water yield.
Adopt treat effluent not adopt fresh water, saved the consumption of fresh water greatly as wash-down water.For reaching developing result and the consumption of saving wash-down water preferably, bed has certain rate of expansion in the time of should guaranteeing to wash, and it is generally acknowledged that rate of expansion at 20%～40% o'clock, can reach satisfied cleaning performance.
Below in conjunction with embodiment effect of the present invention is described.
Embodiment 1 (sorbent material preparation)
The preparation of adsorbent A:
(1) is that 2 natural NaY molecular sieve is a main raw material with the Si/Al atomic ratio, mixes by following part by weight with SB powder, the blue or green powder in field, citric acid and nitric acid: 70: 12: 5: 8: 5.
(2) moulding.Make diameter 1mm by banded extruder, mean length is the fine strip shape of 1.5cm.
(3) roasting.Under 350 ℃, roasting 8 hours.Get adsorbent A.
The preparation of adsorbent B:
(1) be that 3 natural NaY molecular sieve is a main raw material with the Si/Al atomic ratio, the blue or green powder in aluminum hydroxide solid elastomer powder, field, tartrate and the hydrochloric acid produced with aluminium chloride process mix by following part by weight: 75: 10: 3: 4: 8.
(2) moulding.Make diameter 1mm by banded extruder, mean length is the fine strip shape of 1.5cm.
(3) roasting.Under 400 ℃, roasting 6 hours.Get adsorbent B.
The preparation of sorbent material C:
(1) be that 3 natural NaY molecular sieve is a main raw material with the Si/Al atomic ratio, 1: 1 mixture of the blue or green powder of producing with carbon dioxide process in aluminum hydroxide solid elastomer powder, field, acetate and citric acid and nitric acid mix by following part by weight: 65: 15: 4: 8: 8.
(2) moulding.Make diameter 1mm by banded extruder, mean length is the fine strip shape of 1.5cm.
(3) roasting.Under 450 ℃, roasting 4 hours.Get sorbent material C.
Embodiment 2 (adsorbent A is used in cleansing operation)
Referring to accompanying drawing 1 flow process.Ion exchange column is that synthetic glass is made, 6 liters of each post useful volumes, use 4 ion exchange columns during operation, wherein 3 are carried out ion-exchange absorption, 1 is carried out regenerative operation in addition, switch to ion-exchange absorption system after the regeneration, the ion exchange column that contacts with the biochemical treatment water outlet at first simultaneously switches system and carry out regenerative operation.Each ion exchange column is equipped with ion adsorbent 3.75kg, amounts to 15kg.Handle water yield 50L/h, air speed 2.7h
-1Adopt concentration 15% yellow soda ash as regenerated liquid, the regenerated liquid air speed is 0.3h
-1, regeneration period 24h, recovery time 8h (each exchange column work 24h, 8h then regenerates).Device moves 480h altogether.Influent ammonium concentration 25mg/L, water outlet peak concentration 3.6mg/L, mean concns 2.2mg/L, average removal rate 91%.Water inlet calcium ion concn 38mg/L, water outlet mean concns 0.6mg/L, average removal rate 99%.Water inlet magnesium ion concentration 15mg/L, water outlet magnesium ion 0.15mg/L, average removal rate 99%.
Embodiment 3 (adsorbent B is used in cleansing operation)
Other condition is identical with embodiment 2, and influent ammonium concentration is 70mg/L, and calcium ion concn is 70mg/L, and magnesium ion concentration is 30mg/L, adopts concentration 18% yellow soda ash as regenerated liquid.Handling the water yield and air speed remains unchanged.The shortening regeneration period is 8h (1 pillar of every 8h regeneration).As can be seen, although treatment capacity does not reduce, influent ammonia nitrogen and calcium ions and magnesium ions concentration have increased.By shortening the regeneration period, exchange column has still kept the higher removal to ammonia nitrogen and calcium, magnesium ion.Ammonia nitrogen water outlet mean concns 0.98mg/L, average removal rate 98.7%.Water outlet calcium ion mean concns 2.5mg/L, average removal rate 96%, water outlet magnesium ion mean concns 1.0mg/L, average removal rate 97%.
Embodiment 4 (sorbent material C is used in cleansing operation)
Other condition is identical with embodiment 2.At influent ammonium concentration is 25mg/L, calcium 40mg/L, and magnesium 25mg/L, treatment capacity 20L/h, corresponding air speed is 1.1h
-1, exchange capacity is 6.1mg/g, total exchange capacity of ammonium is respectively 69.0g, total exchange capacity 103g of calcium, total exchange capacity 80g of magnesium.Adopt concentration 10% yellow soda ash as regenerated liquid.The pH11 of regenerated liquid～14, it is high that the low back of 1 elder generation appears in ammonia nitrogen in the regenerated liquid, and the trend that reduces gradually again is during regenerated liquid consumption 50L, ammonia nitrogen content is respectively 65g in the regenerated liquid, and the amount that the amount of calcium hydroxide and magnesium hydroxide is converted into calcium ion and magnesium ion is respectively 100g and 78g.The ammonium ion that bears again, calcium ion and magnesium ion account for 94%, 97% and 97% (wt%) of adsorptive capacity respectively.Show on sorbent material substantially and obtained regeneration.
Embodiment 5 (cleaning operation of regeneration back exchange column)
To cleaning through the regenerated exchange column.Flow velocity adopts 0.03m/s, cleans the water yield and amounts to 50L, is 8 times of bed volumetrical.The pH value of cleaning the back rinse water is 8.5, directly qualified discharge.Regeneration period, washing water quantity accounted for 12.5% (wt%) that handles the water yield (50L/h) when being 8h, and the productive rate of clean water is 87.5% (wt%).Regeneration period, washing water quantity accounted for 4% (wt%) that handles the water yield when being 24h, and the productive rate of clean water is 96% (wt%).
Embodiment 6 (processing of regenerated liquid stripping)
Press accompanying drawing 1 flow process, ammonia nitrogen influent concentration 25mg/L, treatment capacity 50L/h.Adopt concentration 15% yellow soda ash as regenerated liquid, the regeneration period is 24h, regeneration liquid measure 50L, and ammonia nitrogen concentration is 500mg/L in the regenerated liquid.Supplying with the stripping tower thermal source is 0.6MPa steam, and regenerated liquid is heated and enters stripping tower, 100 ℃ of column bottom temperatures, 95 ℃ of tower top temperatures.Under the stripping effect, the ammonium in the regenerated liquid goes out from cat head with the form of ammonia, after condensation, becomes 5%～10% industrial ammonia.Take off in the later regenerated liquid of ammonium below the ammonia-nitrogen content 50mg/L, replenish to return behind the new yellow soda ash and recycle.
Claims (10)
1, a kind of treatment process of biochemical treatment water outlet, adopt ion exchange column adsorption cleaning technology, it is characterized in that may further comprise the steps: any placed in-line 1～9 of entering in 2～10 ion exchange columns of biochemical treatment water outlet carries out ion-exchange absorption, other ion exchange column carries out regenerative operation, the exchange column that reaches capacity in the ion exchange column of series connection absorption switches by its terminal valve and adsorption system, and the ion exchange column after the regeneration switches into adsorption system by its terminal valve; Wherein the ion adsorbent that uses in the ion exchange column adopts following process preparation:
(1) is main raw material with the NaY molecular sieve, mixes that the blended weight ratio is 60～80%: 1～20%: 1～10%: 1～10%: 1～10% with aluminium hydrate powder, extrusion aid, organic acid and mineral acid;
(2) moulding;
(3) roasting.
2, in accordance with the method for claim 1, it is characterized in that described ion adsorbent is shaped to diameter 0.5～2mm, length is the fine strip shape of 1～5cm; The roasting condition of described ion adsorbent is: under 300 ℃～500 ℃, and roasting 4～10 hours.
3, in accordance with the method for claim 1, it is characterized in that the NaY molecular sieve that ion adsorbent uses is natural NaY molecular sieve.
4,, it is characterized in that the NaY molecular sieve that ion adsorbent uses is that the Si/Al atomic ratio is 2～5 natural NaY molecular sieve according to claim 1 or 3 described methods.
5, in accordance with the method for claim 1, it is characterized in that employed aluminium hydrate powder in the ion adsorbent preparation process is the aluminium hydrate powder of aluminium chloride process, Tai-Ace S 150 method, carbon dioxide process preparation, and in the SB powder one or more; Employed organic acid is one or more in formic acid, acetate, propionic acid, toxilic acid, citric acid, tartrate, pentanedioic acid, the hexanodioic acid; Employed mineral acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
6, in accordance with the method for claim 1, it is characterized in that the regenerated liquid of the regenerative process use of described ion adsorbent is that concentration is 1～20% sodium carbonate solution, the pH value is 11～14.
7, in accordance with the method for claim 1, behind the regenerated liquid disgorging that it is characterized in that discharging, enter the steam stripped system and regenerate, reuse after the regeneration back replenishes fresh yellow soda ash.
8, in accordance with the method for claim 6, after it is characterized in that ion adsorbent is with sodium carbonate solution regeneration, wash with rinse water, the cleaning flow velocity is 0.01m/s～0.05m/s, the bed expansion rate is 20%～40%, and the consumption of wash-down water accounts for handles 5～10% of the water yield.
9, in accordance with the method for claim 1, the operation air speed that it is characterized in that the waste water adsorption cleaning is 1.0h
-1～5.0h
-1, the regenerated liquid air speed during regeneration is 0.1h
-1～0.5h
-1Water inlet contains the ammonia nitrogen of 10～100mg/L, the calcium ion of 20～100mg/L, the magnesium ion of 20～80mg/L.
10, in accordance with the method for claim 7, it is characterized in that described stripping operational condition is: the working pressure of stripping tower is 0.01～0.1MPa, 90 ℃～100 ℃ of tower top temperatures, 95 ℃～100 ℃ of column bottom temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101049888A CN1259251C (en) | 2003-10-31 | 2003-10-31 | Method for biochemical treatment of discharged water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101049888A CN1259251C (en) | 2003-10-31 | 2003-10-31 | Method for biochemical treatment of discharged water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611451A true CN1611451A (en) | 2005-05-04 |
| CN1259251C CN1259251C (en) | 2006-06-14 |
Family
ID=34757146
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101049888A Expired - Lifetime CN1259251C (en) | 2003-10-31 | 2003-10-31 | Method for biochemical treatment of discharged water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1259251C (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429157C (en) * | 2005-10-31 | 2008-10-29 | 中国石油化工股份有限公司 | Method for treating ammonia nitrogen wastewater |
| CN102070226A (en) * | 2011-01-12 | 2011-05-25 | 上海丰信环保科技有限公司 | Method for absorbing and treating ammonia nitrogen substances in oil refining waste water by utilizing zeolite |
| CN102503016A (en) * | 2011-12-19 | 2012-06-20 | 杭州浙大合力科技有限公司 | Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate |
| CN102050542B (en) * | 2009-10-27 | 2013-06-05 | 中国石油化工股份有限公司 | Deep treatment method for high-concentration organic wastewater |
| CN103288174A (en) * | 2013-06-28 | 2013-09-11 | 武汉科梦环境工程有限公司 | Economic environment-friendly ion exchange technology |
| CN113321339A (en) * | 2021-05-06 | 2021-08-31 | 江南大学 | Method for producing fuel ethanol by recycling evaporated condensed water and reusing evaporated condensed water |
-
2003
- 2003-10-31 CN CNB2003101049888A patent/CN1259251C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100429157C (en) * | 2005-10-31 | 2008-10-29 | 中国石油化工股份有限公司 | Method for treating ammonia nitrogen wastewater |
| CN102050542B (en) * | 2009-10-27 | 2013-06-05 | 中国石油化工股份有限公司 | Deep treatment method for high-concentration organic wastewater |
| CN102070226A (en) * | 2011-01-12 | 2011-05-25 | 上海丰信环保科技有限公司 | Method for absorbing and treating ammonia nitrogen substances in oil refining waste water by utilizing zeolite |
| CN102503016A (en) * | 2011-12-19 | 2012-06-20 | 杭州浙大合力科技有限公司 | Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate |
| CN102503016B (en) * | 2011-12-19 | 2013-09-04 | 杭州浙大合力科技有限公司 | Device and method for treating ammonia nitrogen wastewater, recycling ammonia and preparing ammonium sulfate |
| CN103288174A (en) * | 2013-06-28 | 2013-09-11 | 武汉科梦环境工程有限公司 | Economic environment-friendly ion exchange technology |
| CN113321339A (en) * | 2021-05-06 | 2021-08-31 | 江南大学 | Method for producing fuel ethanol by recycling evaporated condensed water and reusing evaporated condensed water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1259251C (en) | 2006-06-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101234827B (en) | Treatment and resource reclaiming method for chromium-containing wastewater containing high concentration sodium sulfate | |
| CN104129831B (en) | Method for simultaneous removal and recovery of heavy metal ions and organic acid by using chelating resin | |
| CN104261526A (en) | Treatment method of heavy metal wastewater | |
| CN110282783B (en) | Ammonium phosphate chemical wastewater treatment system and method | |
| CN105540971A (en) | Process for crushed coal pressurized gasification industrial wastewater deep processing and high recovery rate | |
| CN1259251C (en) | Method for biochemical treatment of discharged water | |
| CN107804890A (en) | A kind of processing system and its method for improving ammonia nitrogen absorption material absorption property | |
| CN1208260C (en) | Sewage deeply treating process | |
| CN113666561A (en) | High-salt sulfur-containing fluorine-containing wastewater treatment process | |
| CN101054220A (en) | Pre-treatment method for sea salt water | |
| CN1562790A (en) | Method for treating wastewater generated from fabricating nitrophenol as well as for reclaiming and using resources | |
| CN112777774A (en) | Nickel-containing wastewater treatment device and nickel-containing wastewater treatment method | |
| CN104609504A (en) | Method for transfer by ion exchange method, resource recovery and utilization of nitrate nitrogen in water and apparatus thereof | |
| CN1817445A (en) | Regeneration of rare-earth adsorbent after sewage denitrifying and dephosphor | |
| CN106904769B (en) | Method for integrated adsorption and desorption liquid application for removing total nitrogen pollutants in wastewater | |
| CN1093180C (en) | One-step process of resin regeneration and chromium reduction for reclaiming chromium from electroplating waste water | |
| CN112093882B (en) | Method for pretreating binaphthol production wastewater | |
| CN1274406C (en) | Method for preparing deaminating adsorbent | |
| CN211255522U (en) | Nickel-containing wastewater treatment device | |
| CN1485281A (en) | Process of treating ammonia nitrogen waste water by 13X molecular sieve | |
| CN1810663A (en) | Treating process of effluent from N-acetanilide production | |
| CN109467154A (en) | The purification method of coking wastewater | |
| CN111018248B (en) | Treatment method of high-ammonia-nitrogen high-phosphorus-salt wastewater | |
| CN111499055B (en) | Comprehensive treatment method of lithium rubber synthetic wastewater | |
| CN1211298C (en) | Process for treatment of waste water containing boron |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term | ||
| CX01 | Expiry of patent term |
Granted publication date: 20060614 |