CN1119288C - Rectorite adsorbent for treating waste water and its preparing process - Google Patents
Rectorite adsorbent for treating waste water and its preparing process Download PDFInfo
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- CN1119288C CN1119288C CN 01138359 CN01138359A CN1119288C CN 1119288 C CN1119288 C CN 1119288C CN 01138359 CN01138359 CN 01138359 CN 01138359 A CN01138359 A CN 01138359A CN 1119288 C CN1119288 C CN 1119288C
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- rectorite
- adsorbent
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- agent
- salt
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a rectorite adsorbing agent for wastewater treatment and a manufacturing method thereof, which belongs to the field of the separation of liquid by the adsorbing agent. Rectorite ore is used as a main raw material to produce the adsorbing agent. The present invention has the manufacturing method that aluminum salt, or iron salt, or a mixture of the aluminum salt and the iron salt is used as a crosslinking agent, the crosslinking agent is dripped into rectorite suspension liquid under the state of stir, and crosslinking reaction, placing, filtration and drying are carried out to prepare a crosslinking rectorite mixture. A forming agent is added to granulate, and roasting is carried out to prepare the rectorite adsorbing agent. The present invention has the advantages of simple manufacturing method, stable product quality, convenient operation and no secondary pollution. The present invention is an environmental protection product, the adsorption capacity is close to the adsorption capacity of active carbon, but the cost is only from 20% to 35% of the cost of the active carbon. The adsorbing agent of the present invention has good removing effect on inorganic ions, such as heavy metal, cyanogen, etc. and organic compounds. The present invention is suitable for the wastewater treatment of chemical engineering industry, machinery industry, electroplating industry, light industry, printing and dyeing industry, etc.
Description
[technical field]
The present invention relates to a kind of rectorite adsorbent and production method thereof that is used for wastewater treatment, specifically a kind of is the main material production sorbent material with the rectorite leng, be used for the wastewater treatment of industries such as chemical industry, machinery, plating, light industry, printing and dyeing, belong to sorbent material and come the isolating field of treatment liq.
[background technology]
Before the present invention, with sorbent treatment waste water, sewage, adopt gac to make sorbent material as tradition, its weak point is that the production cost of gac is higher, particularly the production of gac need consume a large amount of timber etc., the destruction of causing the forest reserves, ecotope.Also just like adopting atlapulgite to make sorbent material, its weak point is that after the molding, granulating roasting its adsorptive power almost reduces to zero.Remove the heavy metal ion in waste water, the sewage, also have the coagulant precipitation or the chemical precipitation method that more generally adopt,, adjust pH, carry out qualified discharge after the solid-liquid separation by adding coagulating agent and chemical reagent.As to chromate waste water, in " electroplating wastewater is administered and utilized " book of Beijing publication in 1989, Tu Jinbao has introduced still at present adopt ferrite facture and sulfite reduction methods both at home and abroad more, its weak point is that coagulating agent and chemical reagent consumption are big, the processing cost height, and mud can produce secondary pollution.Also have containing the processing of cyanogen root waste water, " electroplating and finish " the 2nd phase in 2000 yellow dimension light has mainly been introduced the external alkaline chlorination process that extensively adopts in " problem that China's electroplating wastewater is administered over 50 years " literary composition, its weak point is containing iron and nickel plasma waste water, use this method very big difficulty is arranged, and need treatment system of design separately, this method is divided into " incomplete oxidation " and " complete oxidation " two steps, domestic owing to limited by automatic instrument(s), only carry out at present " incomplete oxidation ", toxicant cyanate and ammonia that this method produces still can pollute.
[summary of the invention]
The object of the present invention is to provide a kind of rectorite adsorbent and production method thereof that is used for wastewater treatment, can overcome the deficiency of above-mentioned technology, adopting cheap rectorite leng ore deposit is raw material, utilize simple crosslinked intercalation technique, the rectorite adsorbent that is used for wastewater treatment that the production adsorptive power is good, constant product quality, cost are low, easy to use, do not produce secondary pollution.
The present invention provides a kind of rectorite adsorbent that is used for wastewater treatment in order to achieve the above object, it is characterized in that chemical ingredients is by mass percentage: SiO
239.5～43.2, TiO
21.0～3.0, Al
2O
335.3～38.5, Fe
2O
32.3～5.8, CaO 3.8～5.4, MgO 0.1～0.9, K
2O 0.8～1.2, Na
2O 1.0～1.2, and S 0.5～1.2, and surplus is trace element and loss on ignition.
The present invention in order to achieve the above object, a kind of production method that is used for the rectorite adsorbent of wastewater treatment also is provided, adopting the rectorite leng clay is main raw material, it is characterized in that making linking agent with iron carbonyl or oxyaluminum or hydroxyl ferro-aluminum, under the normal temperature and pressure whipped state, it is in 1%～4% the rectorite leng suspension that linking agent is added drop-wise to solid-to-liquid ratio, dosage of crosslinking agent is 0.1～4mmol/g rectorite leng, after the crosslinking reaction 120～240 minutes, left standstill 8～48 hours, filter, obtain the cross-linked rectorite mixture being lower than 80 ℃ of dryings, add calcium salt and ammonium salt forming agent again, addition by mass ratio is: 100% cross-linked rectorite mixture: 10% calcium salt: 5% ammonium salt, through molding, granulating, roasting is made chemical ingredients and is by mass percentage: SiO
239.5～43.2, TiO
21.0～3.0, Al
2O
335.3～38.5, Fe
2O
32.3～5.8, CaO 3.8～5.4, MgO 0.1～0.9, K
2O 0.8～1.2, Na
2O 1.0～1.2, and S 0.5～1.2, and surplus is the rectorite adsorbent of trace element and loss on ignition.
The present invention selects for use cheap natural accumulation supporting stone ore deposit to make raw material, rectorite leng concentrate after purifying or to make raw material through sodium salt activatory rectorite leng concentrate better, utilize rectorite leng to have characteristics such as 1: 1 regular interstratified structure, rectorite leng is activated crosslinking Treatment, produce the rectorite adsorbent that is used for wastewater treatment.The rectorite leng raw material is under the normal temperature and pressure whipped state, after the present invention activates crosslinked production method processing, the rectorite leng interlamellar spacing is brought up to 4.0nm by 2.3nm, its adsorptive power obviously increases, near the adsorptive power of gac, make it become the novel environment friendly material that to remove heavy metal ions in wastewater, cyanogen root and organic compound.But its price only is 20%～35% of a gac.
Used linking agent in the production method of the present invention's series rectorite adsorbent, it is characterized in that with the mixture preparation linking agent that contains aluminium salt, molysite or aluminium salt and molysite, the mixture concentration of aluminium salt, molysite or aluminium salt and molysite is 0.2～1.0mol/L, adjust the pH value of solution value with the NaOH of 0.2～0.5mol/L down in the normal temperature and pressure whipped state, and to keep the pH value be 3.5～5.0, stirred 120～240 minutes, and, made linking agent through leaving standstill hydrolytic polymerization 8～48 hours.Aluminium salt such as aluminum chloride, Tai-Ace S 150 become the multinuclear oxyaluminum through hydrolytic polymerization; Molysite such as ferrous sulfate, ferric sulfate become polymerization iron, multinuclear iron carbonyl through hydrolytic polymerization.Rectorite adsorbent of the present invention adopts the linking agent of aluminium salt and molysite preparation, do not add hazardous and noxious substances, crosslinking reaction is carried out under the normal temperature and pressure whipped state, and composition by changing linking agent and proportioning adsorb optionally that some has the element of recovery value in the waste water.
Forming agent of the present invention is calcium salt and ammonium salt, calcium salt such as lime carbonate, calcium chloride, light calcium carbonate.Ammonium salt such as volatile salt, ammonium chloride, bicarbonate of ammonia.
Rectorite adsorbent of the present invention can be used for removing heavy metals such as Cr, Pb in the waste water, Zn, Ni, Hg, Co, Cu, also can be used for removing the CN in the waste water
-, NH
3-N, NO
3-N, NH
4 +, PO
4 -Deng the COD of mineral ion and sign Organic pollutants, improved the biodegradability of organic pollutant, created good envrionment conditions for follow-up biochemical treatment.Production method of the present invention has that energy consumption is low, power consumption is few, the characteristics of contamination-free discharge, and raw material is from natural clay mineral in addition, and its product is a kind of novel environment friendly material, and production method is a kind of clean preparation method.Handle waste water with rectorite adsorbent of the present invention, can overcome the deficiency of treatment process described in the background technology preferably, to containing heavy metal, chromate waste water particularly, the clearance of Cr (VI) is near 100%, and the rate of recovery of chromium is greater than 95%.Be used for handling and contain CN
-Waste water, CN
-Reduce to 0.014mg/L by 27.2mg/L, under equal condition, with the activated carbon treatment of equivalent, CN
-Reduce to 0.26mg/L by 27.2mg/L, can not produce NH in CNCl and the treating water in the treating processes
3The secondary pollution of-N.Serial rectorite adsorbent of the present invention is optionally removed the organism that contains N, Cl etc. in the waste water, and the waste water of difficult degradations such as aniline, oil of mirbane, p-nitrophenol sodium is had the good treatment effect.Be used to handle aniline waste water (COD is 76600mg/L), the COD clearance is 67.25%, is used for treatment of Nitrobenzene phenol sodium waste water (COD is 130000mg/L), and the COD clearance reaches more than 85%.The invention solves the difficult problem of the deleterious organism difficult treatment of difficult degradation.
The present invention has following outstanding advantage:
1. the invention provides a kind of new rectorite adsorbent material that is used for wastewater treatment, rectorite leng ore deposit with cheapness is a raw material, by crosslinked intercalation technique, make its interlamellar spacing bring up to 4.0nm by 2.3nm, solved an absorption difficult problem that contains the big inorganic group of larger molecular organics and radius in the waste water, its adsorptive power is near acticarbon commonly used, but cost only is 20%～35% of a gac, steady quality, and do not produce secondary pollution.
2. the invention provides a kind of production method that is used for the rectorite adsorbent of wastewater treatment, adopt linking agent to carry out crosslinking reaction, only add aluminium salt and molysite, do not add hazardous and noxious substances, crosslinking reaction is carried out under the normal temperature and pressure whipped state, composition by changing linking agent and proportioning adsorb optionally that some has the element of recovery value in the waste water, improved the biodegradability of organic pollutant, created good envrionment conditions for follow-up biochemical treatment, it is low to have energy consumption, power consumption is few, the characteristics of contamination-free discharge, raw material is from natural clay mineral in addition, and product is a kind of novel environment friendly material, and its production method is a kind of clean preparation method.
3. to be used for the production unit of the rectorite adsorbent of wastewater treatment mainly be mechanical stir-reactor, plate and frame(type)filter press and granulating disc in the present invention; in wastewater treatment process; not only can adopt whip attachment but also can adopt filter bed absorption; filter bed absorption not only can be adopted the rising streaming but also can adopt downflow system; operation is very easy; effluent index is easy to control, and industrial scale is changeable, is easy to realize industrialization.
4. use in waste water treatment rectorite adsorbent of the present invention is to heavy metal, CN
-, PO
4 -3Waste water Deng mineral ion and sign Organic pollutants COD has good removal effect.To containing Cr
6+, Zn
2+Etc. removal rate of heavy metal greater than 99%, to CN
-, PO
4 -3Clearance near 100%, be 7.25%--92% to the COD clearance.
[embodiment]
Embodiment 1: prepare the linking agent that uses in the rectorite adsorbent production of the present invention:
1.1 aluminum chloride is made into 0.4mol/L solution, under the normal temperature and pressure whipped state, drip the NaOH solution of 0.2mol/L, making its pH value is 3.92, and keeps this pH value, stirs 240 minutes, leaves standstill 48 hours, makes the oxyaluminum linking agent.
1.2 ferrous sulfate is made into 1.0mol/L solution, under the normal temperature and pressure whipped state, drip the NaOH solution of 0.2mol/L, making its pH value is 3.5, and keeps this pH value and stirred 120 minutes, leaves standstill 48 hours, makes the iron carbonyl linking agent.
1.3 the mixture of aluminum chloride with 40% and 60% ferrous sulfate is made into 0.5mol/L solution, under the normal temperature and pressure whipped state, drip the NaOH of 0.2mol/L, make its pH value be maintained 3.8, and stirred 120 minutes, left standstill 48 hours, and made hydroxyl ferro-aluminum linking agent.
Embodiment 2: the rectorite adsorbent that is used for wastewater treatment with production method production of the present invention:
Place enamel reaction still 2.1 get purification rectorite leng concentrate 20.0kg; add 500 liters of tap water; under the normal temperature and pressure whipped state; drip the iron carbonyl linking agent; dosage of crosslinking agent is the 4mmol/g rectorite leng; keep pH value 3.5; stirred 150 minutes, left standstill 24 hours; filter; drying obtains the cross-linked rectorite mixture; add calcium chloride and volatile salt again; addition is 100% cross-linked rectorite mixture by mass ratio: 10% calcium chloride: 5% volatile salt, and molding, granulating on granulating disc is produced unequigranular particle then; being lower than 600 ℃ of following roastings, make rectorite adsorbent of the present invention.Its chemical ingredients is by mass percentage: SiO
243.0, TiO
22.9, Al
2O
338.3, Fe
2O
35.7 CaO 5.2, MgO 0.7, K
2O 1.1, Na
2O 1.1, and S 1.2, and surplus is trace element and loss on ignition.
Place enamel reaction still 2.2 get purification rectorite leng concentrate 20.0kg; add 500 liters of tap water; under the normal temperature and pressure whipped state; the oxyaluminum linking agent is added drop-wise in the suspension; dosage of crosslinking agent is the 4mmol/g rectorite leng; after the crosslinking reaction 120 minutes; left standstill 36 hours; filter; obtain the cross-linked rectorite mixture, add lime carbonate and ammonium chloride again, addition is 100% cross-linked rectorite mixture by mass ratio: 10% calcium salt: 5% ammonium salt; molding, granulating on granulating disc then; produce unequigranular particle,, make rectorite adsorbent of the present invention being lower than 600 ℃ of following roastings.Its chemical ingredients is by mass percentage: SiO
243.2, TiO
22.9, Al
2O
337.9, Fe
2O
35.5 CaO 5.4, MgO 0.8, K
2O 1.0, Na
2O 1.1, and S 1.2, and surplus is trace element and loss on ignition.
Embodiment 3: rectorite adsorbent of the present invention is used for the processing of waste water:
3.1 get rectorite adsorbent 0.1kg that embodiment 2.2 produces in the glass column of φ 28 * 1000mm, (the upper and lower quartz sand that 20mm is respectively arranged of sorbent material) contains Cr
6+294.8mg/L the reaction column of waste water through iron filings are housed (flow into the glass column of above-mentioned filling rectorite adsorbent of the present invention behind the φ 34 * 1000mm), continuous 120 hours, flowing liquid volume accumulative total reached 5000mL, and water outlet Cr
6+Concentration only is 0.08mg/L.Carry out same test, water outlet Cr with the alternative rectorite adsorbent of the gac of equivalent
6+Concentration is 0.10mg/L, and the ability specific activity charcoal of visible rectorite adsorbent absorption chromium is slightly strong.
3.2 get rectorite adsorbent 50kg that embodiment 2.2 produces in the stainless steel adsorption tanks of φ 400 * 1000mm, be divided in seven layers of stainless steel mesh, certain factory contains Cr
6+154.8mg/L waste water flow through with the flow velocity of 0.3t/h that (φ 400 * 1000cm) backs flow into the stainless steel adsorption tanks that fill rectorite adsorbent for stainless steel reaction jar that iron filings are housed, operation is 72 hours continuously, and effluent quality reaches the Cr of GB8978-1996 national Specification
6+0.50mg/L content.
3.3 get rectorite adsorbent 50kg that embodiment 2.1 produces in the stainless steel adsorption tanks of φ 400 * 1000mm, be divided in seven layers of stainless steel mesh, get the aniline waste water of certain factory through the pretreated COD8000mg/L of containing.Stainless steel adsorption tanks so that the flow velocity of 0.2t/h is flowed through and filled rectorite adsorbent move 72 hours continuously, and effluent quality COD reduces to 300mg/L.
3.4 get rectorite adsorbent 50kg that embodiment 2.2 produces in the stainless steel adsorption tanks of φ 400 * 1000mm, be divided in seven layers of stainless steel mesh, get certain factory and contain CN
-27.2mg/L waste water adjust pH and be 4.0 after, the stainless steel adsorption tanks so that the flow velocity of 0.3t/h is flowed through and filled rectorite adsorbent move 72 hours continuously, effluent quality CN
-Reduce to 0.014mg/L.
The rectorite adsorbent that the present invention is used for wastewater treatment is a kind of inexpensive novel environment friendly product, because the rectorite leng interlamellar spacing is up to 4.0nm, the more former natural accumulation supporting stone clay of its adsorptive power improves more than 6 times; Production method of the present invention is simple, and constant product quality is easy to use, does not produce secondary pollution, is applicable to industry wastewater treatments such as chemical industry, machinery, plating, light industry, printing and dyeing.
Claims (3)
1, a kind of rectorite adsorbent that is used for wastewater treatment is characterized in that chemical ingredients is by mass percentage: SiO
239.5～43.2, TiO
21.0～3.0, Al
2O
335.3～38.5, Fe
2O
32.3～5.8, CaO 3.8～5.4, MgO 0.1～0.9, K
2O 0.8～1.2, Na
2O 1.0～1.2, and S 0.5～1.2, and surplus is trace element and loss on ignition.
2, a kind of production method that is used for the rectorite adsorbent of wastewater treatment, adopting the rectorite leng clay is main raw material, it is characterized in that making linking agent with iron carbonyl or oxyaluminum or hydroxyl ferro-aluminum, under the normal temperature and pressure whipped state, it is in 1%～4% the rectorite leng suspension that linking agent is added drop-wise to solid-to-liquid ratio, dosage of crosslinking agent is 0.1～4mmol/g rectorite leng, after the crosslinking reaction 120～240 minutes, left standstill 8～48 hours, filter, obtain the cross-linked rectorite mixture being lower than 80 ℃ of dryings, add calcium salt and ammonium salt forming agent again, addition by mass ratio is: 100% cross-linked rectorite mixture: 10% calcium salt: 5% ammonium salt, through molding, granulating, roasting is made chemical ingredients and is by mass percentage: SiO
239.5～43.2, TiO
21.0～3.0, Al
2O
335.3～38.5, Fe
2O
32.3～5.8, CaO 3.8～5.4, MgO 0.1～0.9, K
2O 0.8～1.2, Na
2O 1.0～1.2, and S 0.5～1.2, and surplus is the rectorite adsorbent of trace element and loss on ignition.
3, the production method that is used for the rectorite adsorbent of wastewater treatment according to claim 2, it is characterized in that with the mixture preparation linking agent that contains aluminium salt, molysite or aluminium and molysite, the mixture concentration of aluminium salt, molysite or aluminium salt and molysite is 0.2～1.0mol/L, adjust the pH value of solution value with the NaOH of 0.2～0.5mol/L down in the normal temperature and pressure whipped state, and to keep the pH value be 3.5～5.0, stirred 120～240 minutes, and, made linking agent through leaving standstill hydrolytic polymerization 8～48 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01138359 CN1119288C (en) | 2001-12-28 | 2001-12-28 | Rectorite adsorbent for treating waste water and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01138359 CN1119288C (en) | 2001-12-28 | 2001-12-28 | Rectorite adsorbent for treating waste water and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1356269A CN1356269A (en) | 2002-07-03 |
| CN1119288C true CN1119288C (en) | 2003-08-27 |
Family
ID=4674560
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01138359 Expired - Fee Related CN1119288C (en) | 2001-12-28 | 2001-12-28 | Rectorite adsorbent for treating waste water and its preparing process |
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|---|---|
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398197C (en) * | 2006-08-10 | 2008-07-02 | 武汉理工大学 | Activated inorganic composite catalyst material and its prepn. method |
| CN101791536A (en) * | 2010-04-07 | 2010-08-04 | 西南科技大学 | Method for preparing magnetic rectorite |
| CN102302924A (en) * | 2011-08-18 | 2012-01-04 | 江苏科技大学 | Preparation method of microsphere adsorbent based on rectorite |
| CN103241744A (en) * | 2013-05-23 | 2013-08-14 | 湖北省地质实验研究所 | Modified rectorite clay used as waterproof material and preparation method thereof |
| CN103641245B (en) * | 2013-12-27 | 2016-02-10 | 汕头市龙湖区粤安纸业有限公司 | A kind of paper-making waste water treating agent and preparation method thereof |
| CN103641247B (en) * | 2013-12-27 | 2016-04-06 | 沧州市利达环保工程有限公司 | One way of life sewage-treating agent and preparation method thereof |
| CN104209086B (en) * | 2014-06-13 | 2017-06-27 | 郑州大学 | Can be used to separate the adsorption separating agent and separation method of hexafluoropropene and HFPO mixed gas |
| CN106000359B (en) * | 2016-07-09 | 2018-07-31 | 永春科盛机械技术开发有限公司 | A kind of petrochemical wastewater processing adsorbent and preparation method thereof |
| CN110451770A (en) * | 2019-09-02 | 2019-11-15 | 河南工程学院 | The method for preparing medicament based on iron the pillared rectorite load calper calcium peroxide |
| CN113105595B (en) * | 2021-04-12 | 2022-03-29 | 中国科学院南京土壤研究所 | Cross-linked modified composite material for treating ammonia nitrogen and heavy metal combined pollution wastewater in rare earth mining area and preparation method and application thereof |
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2001
- 2001-12-28 CN CN 01138359 patent/CN1119288C/en not_active Expired - Fee Related
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