CN101708879B - Inorganic-organic composite flocculating agent and preparation method thereof - Google Patents
Inorganic-organic composite flocculating agent and preparation method thereof Download PDFInfo
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- CN101708879B CN101708879B CN2009100562385A CN200910056238A CN101708879B CN 101708879 B CN101708879 B CN 101708879B CN 2009100562385 A CN2009100562385 A CN 2009100562385A CN 200910056238 A CN200910056238 A CN 200910056238A CN 101708879 B CN101708879 B CN 101708879B
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- 239000002131 composite material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000008394 flocculating agent Substances 0.000 title abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 44
- 230000000996 additive effect Effects 0.000 claims abstract description 44
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 26
- 239000010457 zeolite Substances 0.000 claims abstract description 26
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 235000011126 aluminium potassium sulphate Nutrition 0.000 claims abstract description 16
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 16
- 229940050271 potassium alum Drugs 0.000 claims abstract description 16
- GRLPQNLYRHEGIJ-UHFFFAOYSA-J potassium aluminium sulfate Chemical compound [Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRLPQNLYRHEGIJ-UHFFFAOYSA-J 0.000 claims abstract description 16
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 16
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 24
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- 229910000831 Steel Inorganic materials 0.000 claims description 18
- 239000010959 steel Substances 0.000 claims description 18
- 238000005189 flocculation Methods 0.000 claims description 16
- 230000016615 flocculation Effects 0.000 claims description 16
- 235000019353 potassium silicate Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002156 mixing Methods 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 229920002401 polyacrylamide Polymers 0.000 abstract 3
- 239000004115 Sodium Silicate Substances 0.000 abstract 1
- 238000004062 sedimentation Methods 0.000 abstract 1
- 229910052911 sodium silicate Inorganic materials 0.000 abstract 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 4
- 235000011941 Tilia x europaea Nutrition 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000004571 lime Substances 0.000 description 4
- 239000010865 sewage Substances 0.000 description 4
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 3
- 239000011859 microparticle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910001935 vanadium oxide Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003311 flocculating effect Effects 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- -1 sulphur aluminum calcium chloride Chemical compound 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RFZUPEMRDGRJCR-UHFFFAOYSA-K [Al](Cl)(Cl)Cl.[S] Chemical compound [Al](Cl)(Cl)Cl.[S] RFZUPEMRDGRJCR-UHFFFAOYSA-K 0.000 description 1
- CQBLUJRVOKGWCF-UHFFFAOYSA-N [O].[AlH3] Chemical compound [O].[AlH3] CQBLUJRVOKGWCF-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 159000000013 aluminium salts Chemical class 0.000 description 1
- 229910000329 aluminium sulfate Inorganic materials 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000001149 cognitive effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910021432 inorganic complex Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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Abstract
The invention provides an inorganic-organic composite flocculating agent, which comprises the following components in percentage by weight: 90 percent of polyacrylamide, and 5 percent of 4A-zeolite and 5 percent of additive. The additive comprises the following components in percentage by weight: 30 to 50 percent of ammonium sulfate, 30 to 50 percent of sodium sulfate, 5 to 15 percent of sodium silicate, and 5 to 15 percent of potassium alum. The preparation method comprises the following steps: firstly, stirring and mixing the additive; then, mixing the additive with the polyacrylamide (PAM) and the 4A-zeolite to obtain the composite flocculating agent. The flocculating agent has simple production technology, high production capacity, mild reaction conditions, low energy consumption, no three wastes emission; and the composite flocculating agent has quick growth, wide pH application range, quick sedimentation velocity and high COD removal rate.
Description
Technical field
The present invention relates to a kind of chemical industry preparation and preparation method thereof, relate in particular to a kind of inorganic-organic composite coagulator and preparation method thereof.
Background technology
What inorganic at present-organic composite coagulator research was maximum is polymeric aluminum, iron class inorganic polymer and SEPIGEL 305 composite flocculation agent; To its composite condition such as inorganic component and organic constituent ratio, careful research has all been done in aspects such as water treatment condition such as pH value, temperature, stirring velocity and churning time.
China's publication CN1393410A number discloses a kind of organic-inorganic composite flocculant and working method thereof, this kind flocculation agent comprise Dicyanodiamide and formaldehyde polymkeric substance, gather sulphur aluminum chloride and/or gather the sulphur aluminum calcium chloride.Its working method comprises: hydrolysis reaction; Polyreaction and polycondensation.Yet, the toxic substance that adds in this kind method production process, more harsh like formaldehyde to production requirement, and there is certain potentially dangerous property in it.
China's publication CN1821114A number discloses the preparation method of composite flocculation agents such as a kind of Tai-Ace S 150, white lime.This flocculation agent comprises: Tai-Ace S 150, white lime, SEPIGEL 305 positively charged ion and negatively charged ion; Vanadium oxide.Under the state of high chroma sewage, can add gac.Technological process is with Tai-Ace S 150 and white lime uniform mixing; Adding vanadium oxide catalyst again after SEPIGEL 305 positively charged ion and negatively charged ion mixed mixes; The mixture of Tai-Ace S 150 and white lime and SEPIGEL 305 and vanadium oxide mixture remix is even, promptly obtain required flocculation agent.
Common inorganic-the SEPIGEL 305 composite flocculation agent, though can strengthen flocculating effect, improve stability, prolong gelation time, positive charge density is descended to some extent.Usually in sewage or the active sludge, the organic solid particle is electronegative, and the minimizing of composite flocculation agent positive charge density certainly will influence organic removal rate.
The multi-kernel high-molecular inorganic complex compound that multiple inorganic flocculating agent is composited both can increase electric density, can play synergistic function again.Inorganic salt are except molysite and aluminium salt, and silica-based microparticle system also can be used as the raw material of inorganic salt, and its cost is low, and are pollution-free.External more existing reports about silica-based microparticle system and organic polymer composite flocculant, wherein bentonite or montmorillenite microparticle system and positively charged ion polyene acid amides are because its good flocculating effect, commercialization at present.
Summary of the invention
The object of the present invention is to provide a kind of inorganic efficiently-organic composite coagulator and preparation method thereof.
The invention provides a kind of inorganic-organic composite coagulator, it is characterized in that said flocculation agent is by SEPIGEL 305 (PAM), 4A zeolite and additive are formed, and wherein the chemical formula of 4A zeolite is: Na
12Al
12Si
12O
4827H
2O.
Above-mentioned inorganic-organic composite coagulator, wherein, the weight ratio of said SEPIGEL 305,4A zeolite and additive is: 90%: 5%: 5%.
Above-mentioned inorganic-organic composite coagulator, wherein, said additive is made up of ammonium sulfate, sodium sulfate, water glass, potassium alum.
Above-mentioned inorganic-organic composite coagulator, wherein, the weight proportion of described each component of additive is respectively: ammonium sulfate 30～50%, sodium sulfate 30～50%, water glass 5～15%, potassium alum 5～15%.
Above-mentioned inorganic-organic composite coagulator, wherein, the weight proportion of described each component of additive is respectively: ammonium sulfate 35%, sodium sulfate 40%, water glass 15%, potassium alum 10%.
Above-mentioned inorganic-organic composite coagulator, wherein, the weight proportion of described each component of additive is respectively: ammonium sulfate 50%, sodium sulfate 30%, water glass 10%, potassium alum 10%.
Above-mentioned inorganic-organic composite coagulator, wherein, the weight proportion of described each component of additive is respectively: ammonium sulfate 40%, sodium sulfate 45%, water glass 10%, potassium alum 5%.
The present invention also provides a kind of method for preparing inorganic-organic composite coagulator, and said flocculation agent is by SEPIGEL 305, and 4A zeolite and additive are formed, and wherein the chemical formula of 4A zeolite is: Na
12Al
12Si
12O
4827H
2O, it comprises the steps,
Step 1 adds the first steel basin I with additive by selected proportioning, obtains additive agent mixture, after the stirring, is delivered to the second steel basin II;
Step 2 adds the second steel basin II with SEPIGEL 305 and 4A zeolite, adds the additive agent mixture that back has stirred again, after stirring, obtains flocculation agent;
Step 3 is packed the product of second steel basin II output, obtains finished product.
Above-mentioned preparation is inorganic-method of organic composite coagulator, and wherein, the weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%.
Above-mentioned preparation is inorganic-method of organic composite coagulator, and wherein, described stirring at normal temperature condition is: the speed with 25 rev/mins under the normal temperature and pressure stirred 15～25 minutes.
The present invention is through facts have proved, it is simple to have production technique, and throughput is high, and reaction conditions is gentle, energy consumption is low, advantages such as three-waste free pollution, and prepared composite flocculation agent flco generates soon, pH is applied widely, settling velocity is fast and the COD clearance high.
Description of drawings
Fig. 1 be of the present invention inorganic-preparation technology's schema of organic composite coagulator.
Embodiment
Efficient inorganic-organic composite coagulator of the present invention comprises: SEPIGEL 305 (PAM) and 4A zeolite and additive are formed.Wherein the chemical formula of 4A zeolite is Na
12Al
12Si
12O
4827H
2O, the three-dimensional framework shape structural compounds by silica and aluminum-oxygen tetrahedron are formed belongs to isometric system.
The moity of additive of the present invention with and weight part be: ammonium sulfate 30～50%, sodium sulfate 30～50%, water glass 5～15%, potassium alum 5～15%.
Referring to Fig. 1, of the present invention inorganic-preparation technology of organic composite coagulator is:
Step 1 adds the first steel basin I with additive by selected proportioning, stirs 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures, obtains additive agent mixture, and further is delivered to the second steel basin II.
Step 2 adds the second steel basin II with SEPIGEL 305 (PAM) and 4A zeolite, adds the additive agent mixture that back has stirred again, at normal temperatures and pressures with 25 rev/mins speed stirring discharging in 15～25 minutes, obtains the flocculation agent of the finished product.Wherein, the weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%.
Step 3 is packed the product of second steel basin II output, obtains finished product.
Preferably, the present invention can also implement through the proportioning in the following preferred specific embodiment, and obtains different separately wastewater treatment efficiencies.
Embodiment 1:
Additive is added steel basin I by proportioning (ammonium sulfate 35%, sodium sulfate 40%, water glass 15%, potassium alum 10%), stirred 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.SEPIGEL 305 and 4A zeolite are added steel basin II, add the additive that stirs again, the weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%, stirs discharging in 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.Inorganic-organic composite coagulator of preparing is applied to certain sewage work; Advancing dirt mud water ratio is 98.2%; Add according to the invention inorganic-organic composite coagulator 40ppm, mix after the belt sludge dewatering equipment is handled, obtaining the mud extraction water ratio is 84%.
Embodiment 2:
Additive is added steel basin I by proportioning (ammonium sulfate 50%, sodium sulfate 30%, water glass 10%, potassium alum 10%), stirred 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.SEPIGEL 305 and 4A zeolite are added steel basin II, add the additive that stirs again, the weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%, stirs discharging in 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.Inorganic-organic composite coagulator of preparing is applied to certain pig farm WWT, and dosage is 0.3mg/L, and percent of decolourization is 76.5%, COD (COD) clearance 82%, and SS (suspended solids) clearance reaches more than 95%.
Embodiment 3:
Additive is added steel basin I by proportioning (ammonium sulfate 40%, sodium sulfate 45%, water glass 10%, potassium alum 5%), stirred 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.SEPIGEL 305 and 4A zeolite are added steel basin II, add the additive that stirs again, the weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%, stirs discharging in 15～25 minutes with 25 rev/mins speed at normal temperatures and pressures.Inorganic-organic composite coagulator and the Tai-Ace S 150 of preparing composite (inorganic-organic composite coagulator 0.5mg/L, Tai-Ace S 150 100mg/L) is used for the enhanced flocculation of a certain sewage treatment plant inflow, can make COD
CrReduce by 83.4%, BOD5 reduces by 75.8%, and TP (total phosphorus) reduces by 86.2%, and SS reduces by 97.7%.
Above-mentioned specific embodiment is merely several embodiments preferred for this invention; Not will be understood that the present invention only can take above-mentioned several embodiment; All are based on technical characterictic that claim of the present invention limits; And, all should think to fall among protection scope of the present invention in conjunction with routine change or the improved technical scheme that institute in those skilled in the art's the cognitive range can realize.
Claims (7)
1. inorganic-organic composite coagulator is characterized in that, said flocculation agent is by SEPIGEL 305, and 4A zeolite and additive are formed, and the chemical formula of 4A zeolite is: Na
12Al
12Si
12O
4827H
2O; The weight ratio of SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%; Said additive is made up of ammonium sulfate, sodium sulfate, water glass, potassium alum.
2. as claimed in claim 1 inorganic-organic composite coagulator, it is characterized in that the weight proportion of described each component of additive is respectively: ammonium sulfate 30～50%, sodium sulfate 30～50%, water glass 5～15%, potassium alum 5～15%.
3. as claimed in claim 2 inorganic-organic composite coagulator, it is characterized in that the weight proportion of described each component of additive is respectively: ammonium sulfate 35%, sodium sulfate 40%, water glass 15%, potassium alum 10%.
4. as claimed in claim 2 inorganic-organic composite coagulator, it is characterized in that the weight proportion of described each component of additive is respectively: ammonium sulfate 50%, sodium sulfate 30%, water glass 10%, potassium alum 10%.
5. as claimed in claim 2 inorganic-organic composite coagulator, it is characterized in that the weight proportion of described each component of additive is respectively: ammonium sulfate 40%, sodium sulfate 45%, water glass 10%, potassium alum 5%.
6. method for preparing inorganic-organic composite coagulator, said flocculation agent are by SEPIGEL 305, and 4A zeolite and additive are formed, and the chemical formula of 4A zeolite is: Na
12Al
12Si
12O
4827H
2O is characterized in that, comprises the steps,
Step 1 adds first steel basin (I) with additive by selected proportioning, obtains additive agent mixture, after the stirring, is delivered to second steel basin (II);
Step 2 adds second steel basin (II) with SEPIGEL 305 and 4A zeolite, adds the additive agent mixture that back has stirred again, after stirring, obtains flocculation agent;
Step 3 is packed the product of second steel basin (II) output, obtains finished product;
Wherein, the weight ratio of described SEPIGEL 305,4A zeolite and additive is 90%: 5%: 5%, and said additive is made up of ammonium sulfate, sodium sulfate, water glass, potassium alum.
7. preparation as claimed in claim 6 is inorganic-method of organic composite coagulator, and it is characterized in that the agitation condition in described step 1 and the step 2 is: the speed with 25 rev/mins under the normal temperature and pressure stirred 15～25 minutes.
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| CN101708879B true CN101708879B (en) | 2012-02-01 |
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| CN102557218B (en) * | 2011-12-19 | 2013-11-06 | 上海沃杉化工有限公司 | Composite flocculating agent containing various polyacrylamides and preparation method for composite flocculating agent |
| CN104355356B (en) * | 2014-11-20 | 2016-08-24 | 东莞市台腾环保材料科技有限公司 | Sewage-treating agent, preparation method and applications |
| CN108394974A (en) * | 2018-03-20 | 2018-08-14 | 宁波金特信钢铁科技有限公司 | A kind of preparation method of novel inorganic-organic hybrid flocculant |
| CN111875847B (en) * | 2020-07-01 | 2022-05-10 | 中铝山东新材料有限公司 | High-dispersion 4A zeolite, and preparation method and application thereof |
| CN113582310A (en) * | 2021-07-30 | 2021-11-02 | 怀化学院 | Mixed flocculant and preparation method thereof |
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| CN1270931A (en) * | 1999-04-21 | 2000-10-25 | 苏州市建设科技发展有限公司 | Compound water purifying agent for closed water body |
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| CN1483318A (en) * | 2002-09-16 | 2004-03-24 | 北京市建筑材料科学研究院 | Stilbite carrier zine series inorganic germicide |
| CN1994912A (en) * | 2006-12-30 | 2007-07-11 | 吕建荣 | Processing method of heavy metal pickling sewage or acid sewage |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270931A (en) * | 1999-04-21 | 2000-10-25 | 苏州市建设科技发展有限公司 | Compound water purifying agent for closed water body |
| CN1384806A (en) * | 1999-10-06 | 2002-12-11 | 卡米拉卡米股份公司 | Cationic polymers for sludge dewatering |
| CN1483318A (en) * | 2002-09-16 | 2004-03-24 | 北京市建筑材料科学研究院 | Stilbite carrier zine series inorganic germicide |
| CN1994912A (en) * | 2006-12-30 | 2007-07-11 | 吕建荣 | Processing method of heavy metal pickling sewage or acid sewage |
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| Title |
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| JP特开2007-14870A 2007.01.25 |
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