CN1274406C - Method for preparing deaminating adsorbent - Google Patents
Method for preparing deaminating adsorbent Download PDFInfo
- Publication number
- CN1274406C CN1274406C CN 200310104989 CN200310104989A CN1274406C CN 1274406 C CN1274406 C CN 1274406C CN 200310104989 CN200310104989 CN 200310104989 CN 200310104989 A CN200310104989 A CN 200310104989A CN 1274406 C CN1274406 C CN 1274406C
- Authority
- CN
- China
- Prior art keywords
- acid
- accordance
- nay molecular
- water
- molecular sieve
- 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.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000003463 adsorbent Substances 0.000 title claims description 24
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002808 molecular sieve Substances 0.000 claims abstract description 14
- 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 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 5
- 150000007524 organic acids Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims description 14
- 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
- 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
- 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
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 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-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-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
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 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
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 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
- 239000011976 maleic acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 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
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 229910001868 water Inorganic materials 0.000 abstract description 20
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 12
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 12
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 11
- 239000002351 wastewater Substances 0.000 abstract description 11
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 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
- 239000000203 mixture Substances 0.000 abstract description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 abstract description 2
- 239000000498 cooling water Substances 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- 244000275012 Sesbania cannabina Species 0.000 abstract 1
- 239000006096 absorbing agent Substances 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 22
- 239000010457 zeolite Substances 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 21
- 238000001179 sorption measurement Methods 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000004065 wastewater treatment Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- -1 NH 4 + Inorganic materials 0.000 description 3
- 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 3
- 239000003054 catalyst Substances 0.000 description 3
- 229910001603 clinoptilolite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000806 elastomer Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-OUBTZVSYSA-N Ammonia-15N Chemical compound [15NH3] QGZKDVFQNNGYKY-OUBTZVSYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000009372 pisciculture Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 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
- 239000002893 slag Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Landscapes
- Water Treatment By Sorption (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a method for preparing an absorbing agent which can simultaneously removing ammonia nitrogen, calcium ions and magnesium ions in waste water. NaY molecular sieves are used as principal raw material to be uniformly mixed with aluminium hydroxide dry gel powders, sesbania powders, organic acid and inorganic acid, and then, the mixture is shaped and calcined to obtain the adsorbing agent. Compared with common NaY molecular sieves, the ammonium ion absorbing capability of the adsorbing agent prepared by adopting the method of the present invention is improved greatly, and simultaneously, the adsorbing agent can also remove calcium ions and magnesium ions in water. Effluent water can be used as compensation water for circulating cooling water.
Description
Technical field
The present invention relates to a kind of preparation of adsorbent method, especially a kind of preparation of adsorbent method of adsorbing ammonia nitrogen and calcium ion, magnesium ion simultaneously.
Background technology
Nitride is one of major pollutants in the waste water, and the form that exists of nitrogen mainly contains: NH
3, NH
4 +, NO
2, NO
3, organic nitrogen, NH in petrochemical wastewater
4 +The nitrogen of form is main, modal pollutant.Nitrogen in the water makes body eutrophication, thus breed bacteria and algae.
In waste water advanced treatment technology, absorption is effective method, and adsorbent of the prior art has: active carbon, activated coal, carclazyte, diatomite, bentonite, montmorillonite, clay, zeolite, resin, slag, wood chip, coal ash, humic acid etc.The character of various adsorbents is not quite similar, and active carbon is the adsorbent that generally adopts in the present wastewater treatment.Active carbon mainly is the amino molecule (NH in the adsorbed water
3) nitrogen of form, adsorption capacity is limited.NACF is mainly used in and is adsorbed with organic pollutants, and to NH
4 +Adsorbance limited, generally be used for the oil plant comprehensive wastewater and handle.
Zeolite is to NH
4 +Selectivity better, but the adsorption capacity of non-modified zeolite is lower, several various main natural zeolites absorption NH
4 +The effect situation of-N sees Table 1.
Several zeolite NH of table 1
4 +The adsorption capacity of-N
| Zeolite type | The Si/Al atomic ratio | Crystallographic system | mgNH 4 +-N/g zeolite |
| Chabasie | 2 | Tripartite | 5 |
| Modenite | 5 | Quadrature | 2.6 |
| Erionite | 3 | Six sides | 3.8 |
| Clinoptilolite | 4.5 | Monocline | 2.6 |
| A type zeolite | 1 | Cube | 7.0 |
| X type zeolite | 1.25 | Cube | 6.4 |
| Y-type zeolite | 2.0 | Cube | 5.0 |
| T type zeolite | 3.5 | Cube | 3.4 |
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 chloride
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 adsorbance 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 discarded A molecular sieve chloroform, NaOH and the sodium chloride modification of ethene drying, be used for chemical fertilizer factory's nitrogen-containing wastewater, adsorbance reaches 32mgNH
4 +-N/g, but also point out to be applicable to the wastewater treatment that contains potassium ion and calcium ion.NaOH and sodium chloride solution are all adopted in the regeneration of above-mentioned zeolite adsorbents, and cost is higher.CN86106921A is a primary raw material with using natural clinoptilolite or modenite, adding a certain amount of aluminium hydroxide, potassium chloride, NaOH and water mixes, carry out complexity then and become steps such as glue, crystallization for a long time, synthetic a kind of adsorbent, the potassium ion or the ammonium ion that can be used for adsorbed 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 adsorbent, and molecules of ammonia, sulfide and organic matter in the absorption leather-making waste water are not considered NH
4 +The influence of-N adsorption effect.In the prior art, a lot of for the method for modifying of Y zeolite, as acid treatment, hydrothermal treatment consists etc., but be primarily aimed at the modification of the Y zeolite that is used for catalyst, not at carrying out modification as adsorbent.
Summary of the invention
At the deficiencies in the prior art, the purpose of this invention is to provide a kind of wastewater treatment preparation of adsorbent method up to standard of removing ammonia nitrogen, calcium ion, magnesium ion and iron ion simultaneously, the water after the processing can be used for the supplementing water of recirculated cooling water.
Preparation of adsorbent method of the present invention may further comprise the steps:
(1) is primary raw material with the NaY molecular sieve, mixes that the weight ratio of mixing is 60～80%: 1～20%: 1～10%: 1～10%: 1～10% with aluminium hydrate powder, extrusion aid, organic acid and inorganic 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 Alchlor process, aluminum sulfate 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, maleic acid, citric acid, tartaric acid, glutaric acid, the adipic acid etc., and inorganic acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid etc.
The adsorbent employing concentration of the inventive method preparation is 1～20% sodium carbonate liquor regeneration, and adsorption capacity can be recovered more than 90%.
The NH of the natural NaY molecular sieve of handling without the inventive method
4 +-N adsorption capacity is less, is generally about 5.0mg/g, after process the method for the invention is prepared into new adsorbent, and the NH of adsorbent
4 +-N adsorption capacity improves greatly, can reach more than the 30mg/g, and ammonia-N removal rate reached 90w% when above, simultaneously to the clearance of calcium ion and magnesium ion greater than 95w%.Regenerated liquid can effectively be regenerated to adsorbent, recovers the adsorption capacity of adsorbent to ammonia nitrogen, calcium ion and magnesium ion.
The specific embodiment
Below in conjunction with embodiment the solution of the present invention and effect are described.
Embodiment 1
Preparation of adsorbent:
(1) is that 2 natural NaY molecular sieve is a primary 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, average length is the fine strip shape of 1.5cm.
(3) roasting.Under 350 ℃, roasting 8 hours.
Adsorption effect:
The adsorbent of said process preparation is packed in the ion exchange column, 18 liters of post dischargeable capacitys, ion exchange column is equipped with adsorbent 12kg, handles water yield 50L/h, and the regeneration period is 16h, air speed 2.7h
-1Adopting concentration is the regeneration of 15% sodium carbonate liquor.Influent ammonium concentration 2905mg/L, dynamically ammonia nitrogen exchange capacity 34.17mgNH
4 +-N/g.Water inlet calcium ion concentration 38mg/L, water outlet mean concentration 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 2
Preparation of adsorbent:
(1) be that 3 natural NaY molecular sieve is a primary raw material with the Si/Al atomic ratio, the blue or green powder in aluminum hydroxide solid elastomer powder, field, tartaric acid and the hydrochloric acid produced with Alchlor process mix by following part by weight: 75: 10: 3: 4: 8.
(2) moulding.Make diameter 1mm by banded extruder, average length is the fine strip shape of 1.5cm.
(3) roasting.Under 400 ℃, roasting 6 hours.
Adsorption effect:
Other condition is identical with embodiment 1, and the rising influent ammonium concentration is to 3874mg/L, and calcium ion concentration is to 70mg/L, and magnesium ion concentration is to 30mg/L, and adopting concentration is the regeneration of 20% sodium carbonate liquor.Handling the water yield and air speed remains unchanged.Regeneration period is 16h.Dynamic ammonia nitrogen exchange capacity 33.66mgNH
4+-N/g.Water outlet calcium ion mean concentration 2.5mg/L, average removal rate 96%, water outlet magnesium ion mean concentration 1.0mg/L, average removal rate 97%.
Embodiment 3
Preparation of adsorbent:
(1) be that 3 natural NaY molecular sieve is a primary 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, average length is the fine strip shape of 1.5cm.
(3) roasting.Under 450 ℃, roasting 4 hours.
Adsorption effect:
At influent ammonium concentration is 4855mg/L, calcium 40mg/L, and magnesium 25mg/L, treating capacity 20L/h, corresponding air speed is 1.1h
-1, the regeneration period is when being 24h.Adopting concentration is the regeneration of 18% sodium carbonate liquor.Regeneration period is 16h.Dynamic ammonia nitrogen exchange capacity 38.16mgNH
4 +-N/g.Water outlet calcium ion mean concentration 2.5mg/L, average removal rate 96%, water outlet magnesium ion mean concentration 1.0mg/L, average removal rate 97%.
Claims (7)
1, a kind of ammonium preparation of adsorbent method of taking off may further comprise the steps:
(1) is primary raw material with the NaY molecular sieve, mixes that the weight ratio of mixing is 60～80%: 1～20%: 1～10%: 1～10%: 1～10% with aluminium hydrate powder, extrusion aid, organic acid and inorganic acid;
(2) moulding;
(3) roasting was 300 ℃～500 ℃ following roastings 4～10 hours.
2, in accordance with the method for claim 1, it is characterized in that described forming process of (2) step is: make diameter 0.5～2mm on banded extruder, length is the fine strip shape of 1～5cm.
3, in accordance with the method for claim 1, it is characterized in that described NaY molecular sieve is natural NaY molecular sieve.
4, in accordance with the method for claim 1, the Si/Al atomic ratio that it is characterized in that described natural NaY molecular sieve is 2～5.
5, in accordance with the method for claim 1, it is characterized in that described aluminium hydrate powder is the aluminium hydrate powder of Alchlor process, aluminum sulfate method, carbon dioxide process preparation, and in the SB powder one or more.
6, in accordance with the method for claim 1, it is characterized in that described organic acid is one or more in formic acid, acetate, propionic acid, maleic acid, citric acid, tartaric acid, glutaric acid, the adipic acid.
7, in accordance with the method for claim 1, it is characterized in that described inorganic acid is one or more in hydrochloric acid, sulfuric acid, nitric acid, the phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104989 CN1274406C (en) | 2003-10-31 | 2003-10-31 | Method for preparing deaminating adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200310104989 CN1274406C (en) | 2003-10-31 | 2003-10-31 | Method for preparing deaminating adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1611294A CN1611294A (en) | 2005-05-04 |
| CN1274406C true CN1274406C (en) | 2006-09-13 |
Family
ID=34757147
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200310104989 Expired - Lifetime CN1274406C (en) | 2003-10-31 | 2003-10-31 | Method for preparing deaminating adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1274406C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460058C (en) * | 2006-01-20 | 2009-02-11 | 王家强 | Modified natural and self-making floating carrier and mesopore molecular sieve denitrogen dephosphorus material, its preparation and application |
| CN101007261B (en) * | 2006-12-17 | 2010-05-12 | 于向真 | Zeolite adsorbent and its preparation method |
| CN102078820B (en) * | 2009-11-27 | 2013-01-09 | 中国石油化工股份有限公司 | Method for reducing ammonium and nitrogen consumption in FCC (Fluid Catalytic Cracking) catalyst production process |
| CN102794191B (en) * | 2011-05-26 | 2014-07-30 | 中国石油化工股份有限公司 | Method for preparing catalytic cracking catalyst |
| CN102794194B (en) * | 2011-05-26 | 2014-07-30 | 中国石油化工股份有限公司 | Method for preparing catalytic cracking aid |
| CN103055833B (en) * | 2013-01-15 | 2015-06-24 | 苏州工业园区安泽汶环保技术有限公司 | Preparation method of ammonia removal material |
-
2003
- 2003-10-31 CN CN 200310104989 patent/CN1274406C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1611294A (en) | 2005-05-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101007261B (en) | Zeolite adsorbent and its preparation method | |
| CA2386358C (en) | Zeolite adsorbents, method for obtaining them and their use for removing carbonates from a gas stream | |
| Yang et al. | In-situ preparation of NaA zeolite/chitosan porous hybrid beads for removal of ammonium from aqueous solution | |
| CN1311713A (en) | Molecular sieve adsorbent for gas purification and preparation thereof | |
| EP1150763A1 (en) | Method for simultaneously abating nitric oxides and nitrous oxides in gases containing them | |
| TR201816382T4 (en) | Agglomerated zeolitic adsorbents, processes for their preparation and their use. | |
| CN105289470A (en) | Method for preparing charcoal-supported attapulgite nano composite by using antibiotic wastewater | |
| CN101234792B (en) | Method for removing fluorine ion from water by using oxide of lanthanum-carried aluminum oxide | |
| JP2002154821A (en) | Apparatus and method for purifying gas | |
| Eturki et al. | Use of clay mineral to reduce ammonium from wastewater. Effect of various parameters | |
| CN1274406C (en) | Method for preparing deaminating adsorbent | |
| CN111013556B (en) | High-selectivity resin capable of synchronously adsorbing fluorine and phosphorus, and synthetic method and application thereof | |
| Wu et al. | Succinic acid-assisted modification of a natural zeolite and preparation of its porous pellet for enhanced removal of ammonium in wastewater via fixed-bed continuous flow column | |
| CN103721682A (en) | Absorbent for purifying benzene-containing waste gas and preparation method of absorbent | |
| WO2010109477A2 (en) | A process for the preparation of molecular sieve adsorbent for the size/shape selective adsorption of carbon dioxide from its gaseous mixture with nitrogen | |
| Zolfaghari et al. | Surface modification of ordered nanoporous carbons CMK-3 via a chemical oxidation approach and its application in removal of lead pollution from water | |
| Canellas et al. | Removing ammonia from wastewater using natural and synthetic zeolites: A batch experiment | |
| WO2010113173A2 (en) | A barium and potassium exchanged zeolite-x adsorbents for co2 removal from a gas mixture and preparation thereof | |
| CN1259251C (en) | Method for biochemical treatment of discharged water | |
| JPH1150069A (en) | Purification of natural gas | |
| CN1085114C (en) | Catalyst for purifying nitrogen-contained gas to remove carbon monoxide and course thereof | |
| CN1485281A (en) | Process of treating ammonia nitrogen waste water by 13X molecular sieve | |
| CN112191223A (en) | Modified zeolite filter material for treating phosphorus-containing industrial discharge water and preparation method thereof | |
| CN1279037C (en) | Method for removing corrosive impurity from inferior sulfolane | |
| CN113000020B (en) | Adsorbent for ink sewage purification, preparation method, application and regeneration method |
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: 20060913 |