CN1325391C - Method of producing poly aluminium iron silicate composite flocculating agent using fly ash and ferrous sulphate - Google Patents
Method of producing poly aluminium iron silicate composite flocculating agent using fly ash and ferrous sulphate Download PDFInfo
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- CN1325391C CN1325391C CNB2006100541436A CN200610054143A CN1325391C CN 1325391 C CN1325391 C CN 1325391C CN B2006100541436 A CNB2006100541436 A CN B2006100541436A CN 200610054143 A CN200610054143 A CN 200610054143A CN 1325391 C CN1325391 C CN 1325391C
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Abstract
The present invention belongs to a polymeric flocculating reagent for water treatment, and more specifically, the present invention relates to a method for preparing a polymeric aluminum iron silicate composite flocculating reagent by using pulverized coal ash and ferrous sulfate heptahydrate, and the method comprises the steps of preparation of a primary product, impregnation of the primary product and separation of a product. The method provides new production technology which is characterized in that solid waste produced by a coal-fired power plant, namely the pulverized coal ash, and a byproduct in the production of titanium white powder, namely the ferrous sulfate heptahydrate, are used as main raw material to prepare the composite flocculating reagent with high efficiency; in this way, the problems of low utilization rate of the raw material, poor stability of the products and product incapacitation because reactive silicate is easily flocculated are solved, and the production technology has the advantages of simplified technologic process, greatly shortened production time, less investment, low operating cost, high stability of the products and good performance of the products. Besides, a new path for the utilization of the pulverized coal ash and the byproduct in the production of the titanium white powder, namely the ferrous sulfate heptahydrate, the comprehensive utilization ratio of resources is raised, and the production cost of a polymeric aluminum iron silicate and the cost of sewage treatment are reduced; therefore, the method has high economic benefits, environmental protection benefits and social benefits.
Description
One, technical field
The invention belongs to the water treatment polymeric flocculant, be specifically related to the preparation method of poly aluminium iron silicate.
Two, background technology
At present, the polymeric aluminium-silica flocculation agent of developing is broadly divided into two classes both at home and abroad: a class is to introduce the product of making behind the silicon in polyaluminium sulfate, as polymerized aluminium sulfate flocculant (PASS); Another kind of is based on activated silicic acid, adds the product of making after the aluminium salt, as polymer aluminium silicate salt (PSAS).The former preparation technology is comparatively complicated, and raw material, equipment are all had higher requirement; Latter preparation technology is simple, inexpensive, but effective concentration content is lower, and less stable is difficult to commercialization, only is suitable for water factory's on-site preparation and adds.Poly silicate aluminium ferric flocculating agent is the composite flocculation agent that grows up on the basis of gathering flocculation agents such as silicic acid and conventional aluminum salt, molysite, has the effect of charge neutrality adsorption bridging, and flocculating effect is good, receives the very big concern of field of water treatment.
At present, the annual emissions of China's coal-burning power plant's flyash has reached more than 100,000,000 ton, and its utilization ratio only is about 30%, and a large amount of flyash are piled up in ash, have not only taken a large amount of land resources, and severe contamination environment.Therefore, the comprehensive utilization of flyash is one of popular topic in the environmental protection research field always.How fully to develop flyash, improve the added value of its utilization, making it turns waste into wealth, and this is the difficult problem that the current techniques field will solve.
Because flyash and poly aluminium iron silicate have similar elementary composition, it is the method for feedstock production poly aluminium iron silicate that related scientific research worker has explored with flyash.
Had a denomination of invention open for the Chinese invention patent application of " the special synthesis technique of poly aluminium iron silicate " on March 16th, 2005, publication number is CN1594082A.Its major technique content is: with flyash and ironmaking slag is main raw material, and preparation technology has comprised totally eight step processes such as the preparation of polymeric ferric aluminum, the preparation of polymeric silicicacid and the preparation of polymeric aluminium ferrum silicate.There is following weak point in this technology: its employed supplementary material component is more, includes flyash, ironmaking slag, sodium hydroxide, yellow soda ash, sulfuric acid and hydrochloric acid; And raw material there is particular requirement, Fe
2O
3Content is the ironmaking waste residue 20-40% of 40-50%, Fe
2O
3Content is 4%-10%, Al
2O
3Content is 20-30%, SiO
2Content is the flyash of 40-60%; Complex technical process, the preparation condition harshness need be carried out under certain pressure condition (0.5-0.6MPa).Therefore, if be used for industrialization, its technological equipment investment expense, production operation expense etc. are all higher, and it is too high to be used for cost for wastewater treatment.
Three, summary of the invention
The objective of the invention is to above-mentioned defective at the prior art existence, plan provides a kind of method with flyash and ferrous sulfate production poly aluminium iron silicate composite flocculating agent that is different from the prior art scheme, it is few to make it the auxiliary agent kind, technological process and condition are simple, the investment of production equipment expense is less, process cost is low, and product performance are stable, and are superior in quality.
For realizing purpose of the present invention, the technical scheme of being taked is as follows.
A kind of method of producing poly aluminium iron silicate composite flocculating agent with flyash and ferrous sulfate comprises that with flyash be raw material, it is characterized in that it is made up of three step processes:
(1) preparation of primary products
With flyash, ferrous sulfate, calcined soda for industry by weight 1: 0.8～1.2: 0.5～0.8 thorough mixing, again with mixture under 800-900 ℃ of temperature condition, roasting 0.5-2 hour, be primary products behind the naturally cooling.
(2) dipping of primary products
The technical hydrochloric acid that primary products that step () is made and volume ratio are 1: 1 stirred dipping 2-4 hour by weight 1: 5～20 under 40-90 ℃ of temperature condition, the still aging 1-2 of room temperature hour then.
(3) product separation
Impregnation product after step (two) ageing is carried out centrifuging separate, filtrate is the aluminium silicate polymer iron product; Filter residue is unreacted flyash, returns in the step () as raw material to recycle.
The present invention is by the previous process steps products obtained therefrom, and the solid solubility rate reaches 90%-95%, does not occur gel in 3 months, and product performance are more stable.
The aluminium silicate polymer iron product that the inventive method is prepared, handle floc test by simulation and actual paper waste, the result shows that this product flocculating effect is good, settling time is short, has the effect of decolouring preferably and removing COD than like product, percent of decolourization is 92.9%, and the COD clearance is 84.1%, is a kind of novel water treatment composite flocculant.
The inventive method compared with prior art, it is main raw material that a by-product ferrous sulfate during with coal-burning power plant's solid waste coal ash and production titanium dioxide is provided, the new production process of the efficient composite flocculation agent of preparation poly aluminium iron silicate, it is low to have solved raw material availability, product stability is poor, and reactive silicate forms the problem that gel causes product failure easily; Simplify technological process, shortened the production time greatly, less investment, process cost is low, and product stability is good, excellent property; Utilization for flyash and the by-product ferrous sulfate during of producing titanium dioxide simultaneously provides new approach, improved the comprehensive utilization of resources rate, also reduce the production cost and the cost of sewage disposal of poly aluminium iron silicate, had very strong economic benefit, environmental benefit and social benefit.
Four, embodiment
Enumerate the embodiment that a plurality of embodiment further specify the inventive method below, and the good result of embodiment product treatment paper waste.It is to be noted that the inventive method is not limited to illustrated embodiment.
Embodiment 1
Take by weighing 2.5Kg flyash, 2.5Kg ferrous sulfate and 1.5Kg soda ash thorough mixing, with its roasting 50 minutes under 850 ℃ of conditions, be chilled to room temperature certainly then, primary products.
The technical hydrochloric acid 70Kg that with the primary products volume ratio is 1: 1 flooded 3 hours under 80 ℃ of temperature condition, still aging 2 hours of room temperature, and centrifuging gets the liquid product poly aluminium iron silicate, and product is preserved and was not occurred gel in 3 months.
Embodiment 2
Take by weighing 2.5Kg flyash, 2.5Kg gram ferrous sulfate and 2Kg gram soda ash thorough mixing, with its roasting 40 minutes under 850 ℃ of conditions, be chilled to room temperature certainly then, primary products.
The technical hydrochloric acid 80Kg that with the primary products volume ratio is 1: 1 is in 70 ℃ of temperature condition dipping 3 hours down, still aging 2 hours of room temperature, and centrifuging gets the liquid product poly aluminium iron silicate, and product is preserved and was not occurred gel in 3 months.
Embodiment 3
Take by weighing 2.5Kg flyash, 2.5Kg ferrous sulfate and 2Kg soda ash thorough mixing, with its roasting 30 minutes under 850 ℃ of conditions, be chilled to room temperature certainly then, primary products.
The technical hydrochloric acid 80Kg that with the primary products volume ratio is 1: 1 is in 60 ℃ of temperature condition dipping 3 hours down, still aging 1 hour of room temperature, and centrifuging gets the liquid product poly aluminium iron silicate, and product is preserved and was not occurred gel in 3 months.
Embodiment 4
With the preservation of embodiment 3 preparation product poly aluminium iron silicate and the commercial like product after at least 2 months be used to handle actual paper waste contrast experiment, result such as following table:
| CODmg·L 1 | Rest COD mgL 1 | Clearance % | Colourity/doubly | Residue colourity/doubly | Percent of decolourization | |
| Poly aluminium iron silicate | 378 | 60 | 84.1 | 280 | 20 | 92.9％ |
| PAC | 378 | 74 | 80.4 | 280 | 35 | 87.5％ |
| PFS | 378 | 78 | 79.4 | 280 | 40 | 85.7％ |
Annotate: PAC, PFS are respectively commercially available polymerize aluminum chloride, bodied ferric sulfate.
Can find that by the contrast experiment poly aluminium iron silicate is compared with commercial like product polymerize aluminum chloride, bodied ferric sulfate, has the effect of decolouring preferably and removing COD.It is little to find also that in treatment of simulated sewage and papermaking wastewater, sanitary sewage experiment poly aluminium iron silicate has a dosage, and alumen ustum is big and closely knit, the sedimentation of flco stratification, and settling velocity is fast, the characteristics that treatment effect is good.
Claims (1)
1, a kind of method of producing poly aluminium iron silicate composite flocculating agent with flyash and ferrous sulfate, comprise that with flyash be raw material, it is characterized in that it is made up of three step processes: the preparation of (one) primary products, with flyash, ferrous sulfate, calcined soda for industry by weight 1: 0.8～1.2: 0.5～0.8 thorough mixing, again with mixture under 800-900 ℃ of temperature condition, roasting 0.5-2 hour, be primary products behind the naturally cooling; (2) dipping of primary products, the technical hydrochloric acid that primary products that step () is made and volume ratio are 1: 1 stirred dipping 2-4 hour by weight 1: 5～20 under 40-90 ℃ of temperature condition, the still aging 1-2 of room temperature hour then; (3) product separation carries out centrifuging with the impregnation product after step (two) ageing and separates, and filtrate is the aluminium silicate polymer iron product, and filter residue returns step () and recycles as raw material.
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| CNB2006100541436A CN1325391C (en) | 2006-03-17 | 2006-03-17 | Method of producing poly aluminium iron silicate composite flocculating agent using fly ash and ferrous sulphate |
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| CN1325391C true CN1325391C (en) | 2007-07-11 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101746868B (en) * | 2008-12-17 | 2013-05-29 | 沈阳工业大学 | Composite flocculant for treating oily wastewater |
| CN101830477B (en) * | 2010-06-10 | 2012-12-05 | 济宁医学院 | Technology for preparing PSAF (Polymer Silica Aluminum Ferrum) by waste rock base raw material |
| CN102557208A (en) * | 2011-03-10 | 2012-07-11 | 中国环境科学研究院 | Method for preparing poly aluminum ferric silicate composite flocculating agent by using red mud and ferrous sulfate |
| CN103265102B (en) * | 2013-06-07 | 2014-07-02 | 嘉善海峡净水灵化工有限公司 | Process for recycling filter residues of multi-core aluminium-polyaluminium silicate phosphide chloride |
| CN103420384B (en) * | 2013-08-08 | 2014-12-03 | 陕西科技大学 | Comprehensive utilization method for coal ash solid waste |
| CN103466774A (en) * | 2013-10-10 | 2013-12-25 | 兰州理工大学 | Method for producing compound coagulant by using fly ash |
| CN104261539B (en) * | 2014-10-08 | 2015-12-02 | 西安石油大学 | The method of water purification agent is prepared with waste |
| CN109809541B (en) * | 2017-11-20 | 2021-09-24 | 临沂大学 | Polymeric aluminum ferric silicate flocculant and preparation method thereof |
| CN110791657A (en) * | 2019-08-22 | 2020-02-14 | 攀枝花火凤凰再生资源回收利用有限责任公司 | Comprehensive utilization method of multiple elements in sintering dust collection ash of steel plant |
| CN110526364B (en) * | 2019-09-25 | 2021-12-17 | 仲恺农业工程学院 | Method for preparing poly-aluminum ferric silicate flocculant by utilizing waste incineration fly ash |
| CN111019693A (en) * | 2019-12-05 | 2020-04-17 | 渭南师范学院 | Universal diesel oil decoloring deodorant and preparation and regeneration method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328970A (en) * | 2000-06-15 | 2002-01-02 | 中国科学院地球化学研究所 | Cleaning agent of aqueous aluminium iron polysilicate waste water and its production method |
| CN1594082A (en) * | 2004-07-14 | 2005-03-16 | 华北工学院分院 | Special synthesis process of poly ferrum aluminium silicate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1328970A (en) * | 2000-06-15 | 2002-01-02 | 中国科学院地球化学研究所 | Cleaning agent of aqueous aluminium iron polysilicate waste water and its production method |
| CN1594082A (en) * | 2004-07-14 | 2005-03-16 | 华北工学院分院 | Special synthesis process of poly ferrum aluminium silicate |
Non-Patent Citations (1)
| Title |
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| 粉煤灰制备聚硅酸铝铁及条件选择 朱开金，化工环保，第24卷 2004 * |
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