CN100554177C - A kind of preparation method of polymerized ferric-aluminum chloride composite coagulating agent - Google Patents
A kind of preparation method of polymerized ferric-aluminum chloride composite coagulating agent Download PDFInfo
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- CN100554177C CN100554177C CNB200710042744XA CN200710042744A CN100554177C CN 100554177 C CN100554177 C CN 100554177C CN B200710042744X A CNB200710042744X A CN B200710042744XA CN 200710042744 A CN200710042744 A CN 200710042744A CN 100554177 C CN100554177 C CN 100554177C
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- hydrochloric acid
- waste liquor
- calcium aluminate
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- acid pickling
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Abstract
The present invention relates to a kind of preparation method of inorganic polymer coagulant, especially utilize hydrochloric acid pickling waste liquor and calcium aluminate powder to prepare the preparation method of polymerized ferric-aluminum chloride composite coagulating agent, belong to technical field of chemistry and chemical engineering.Characteristics of the present invention are: according to hydrochloric acid pickling waste liquor free acid content and iron-holder, and control Fe wherein
2+Concentration is 75～90g/L, is source of iron with it; Adopting calcium aluminate powder again is the aluminium source, Al wherein
2O
3Content is 47～56%; In the mass ratio of calcium aluminate powder and hydrochloric acid pickling waste liquor is that 0.05～0.10 ratio puts into both raw materials in reactor, and stirring reaction is 1～3 hour under 50～80 ℃ of temperature; In reaction process, add small amounts of chlorine Barbiturates oxygenant and phosphate stabilizer; The heated and stirred reaction, reaction finishes, and is cooled to room temperature, promptly gets the liquid polymeric ferric-aluminum chloride composite coagulating agent.This product is mainly used in the purifying treatment of sanitary sewage and trade effluent.Technology of the present invention is simple, and is the open approach of comprehensive utilization of hydrochloric acid pickling waste liquor.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic polymer coagulant, especially utilize hydrochloric acid pickling waste liquor and calcium aluminate powder to prepare the preparation method of polymerized ferric-aluminum chloride composite coagulating agent, belong to technical field of chemistry and chemical engineering.
Background technology
For improving the steel surface structure or processing treatment being carried out on the surface, often utilize the corrosive nature of strong acid that steel surface is cleaned, to remove the corrosion thing of steel surface, and when cleaning proceeds to a certain degree, acid concentration reduces in the washing lotion, pickling speed slows down, and must change eo-acid to keep suitable pickling speed, and residual liquor discharge promptly forms the spent pickle liquor that contains high-concentration metallic ions and residual acid.The H that generally contains 0.05～5g/L in the spent pickle liquor
+Fe with 60～250g/L
2+, nearly hundred ten thousand steres of the annual spent pickle liquor quantity discharged of China.Because spent pickle liquor can cause severe contamination to environment, has been listed in Hazardous wastes at present and has managed.Because traditional treatment process can produce a large amount of body refuses and waste resource, in recent years to having obtained paid certain attention and research in the processing of steel pickling waste liquor and the comprehensive utilization, one of them main aspect is exactly to utilize it as the raw material of producing inorganic coagulant, as preparation poly-ferric chloride, bodied ferric sulfate, aluminium iron polychloride etc.
Iron aluminium compound coagulant is a kind of novel inorganic high-molecular coagulant adopting that the seventies research and development is got up, it has advantages such as the settling velocity of the good coagulation performance of aluminium salt and molysite is fast, absorption property is strong, and has overcome that the water outlet of molysite is unclear, colourity is high and the alumen ustum of aluminium salt generates shortcomings such as slow, that alumen ustum is light.
Utilize spent pickle liquor (sulfuric acid pickling waste liquid or hydrochloric acid pickling waste liquor) preparation poly-ferric chloride, bodied ferric sulfate, the existing many patents of aluminium iron polychloride coagulating agent and document, as Chinese patent application number be 200510101065.6,02115953.X, CN99102960.7,93118752.4,88105465.8 patent documentation.But the product of these patents and bibliographical information or be to be the poly-iron coagulating agent of one-component with the molysite, or be ferro-aluminum compound coagulant based on aluminium salt.Polymerized ferric-aluminum chloride composite coagulating agent based on molysite yet there are no report.And with spent pickle liquor and calcium aluminate powder is that feedstock production composite coagulant polymeric ferric-aluminum chloride composite coagulating agent does not appear in the newspapers yet.
Utilize spent pickle liquor and calcium aluminate powder to be feedstock production composite coagulant polymeric ferric-aluminum chloride, both can bring into play the strong point of iron, aluminium coagulating agent, can overcome shortcoming again from each.Both the comprehensive utilization for spent pickle liquor provided a kind of feasible way, can be the coagulating agent production cheap production technique of supplying raw materials again, reached the purpose of the treatment of wastes with processes of wastes against one another, had good economic benefits, social benefit and environmental benefit.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing hydrochloric acid pickling waste liquor and calcium aluminate powder to prepare polymerized ferric-aluminum chloride composite coagulating agent for main raw material.
The preparation method of a kind of polymerized ferric-aluminum chloride composite coagulating agent of the present invention is characterized in that technological process and step that having of this method is following:
A. the preparation of raw material: adopting hydrochloric acid pickling waste liquor and calcium aluminate powder is main raw material; Fe2+ concentration in the hydrochloric acid pickler is 75～90g/L; Al in the calcium aluminate powder
2O
3Content is 47～56%;
B. get a certain amount of hydrochloric acid pickling waste liquor and be positioned in the reactor, under 50～80 ℃ of temperature and agitation condition, add the chloric acid saline oxidizing agent in batches, make ferrous ion all be oxidized to ferric ion;
C. be that 0.05～0.10 ratio adds calcium aluminate powder in the mass ratio of calcium aluminate powder and hydrochloric acid pickling waste liquor then, stirring reaction is 1～3 hour under 50～80 ℃ of temperature, aluminium in the material is dissolved in the liquid phase and with iron ion to greatest extent carries out composite polymeric;
D. filtered while hot then, filtrate, and in P/[Fe+Al] ratio of mol ratio=0.05～0.15 adds phosphoric acid salt or biphosphate salt stabilizing agent, the continuation stirring reaction in filtrate; Reaction finishes, and is cooled to room temperature, promptly gets the liquid polymeric ferric-aluminum chloride composite coagulating agent.
Fe in the hydrochloric acid pickling waste liquor described in the present invention
2+Concentration is 75～85g/L; Al in the described calcium aluminate powder
2O
3Content is 50～55%; The mass ratio of described calcium aluminate powder and hydrochloric acid pickling waste liquor is 0.07～0.09; The temperature of reaction of described stirring reaction is 60～75 ℃; Reaction times is 1.5～2.5 hours.The inventive method has following advantage and characteristics:
(1) the present invention utilizes spent pickle liquor and calcium aluminate powder to be raw material, can reduce the manufacturing cost of polymerized ferric-aluminum chloride greatly; Because this product is mainly used in the purifying treatment of sanitary sewage and trade effluent, therefore also can reduce the cost of wastewater treatment greatly; And help applying of this novel coagulating agent.
(2) spent pickle liquor is fully utilized, when reducing the inorganic polymer coagulant production cost, can improve its environmental value again, reach treatment of wastes with processes of wastes against one another purpose, realize the resource utilization and the comprehensive utilization of spent pickle liquor.
(3) ferrous content can influence its water treatmenting performance in the polymerization iron aluminium coagulating agent, adopts the high chlorate oxidizer of oxidation equivalent, can be oxidation of divalent iron ion ferric ion effectively, makes Fe in the product
2+Ionic concn is lower than 0.1%.
(4) adopt phosphoric acid salt as stablizer, can overcome the unsettled shortcoming of polymerization iron aluminium coagulating agent, make product have satisfactory stability, can not produce precipitation.
(5) the inventive method technology is simple, and is easy and convenient to handle, the polymerized ferric-aluminum chloride coagulating agent excellent property that makes, steady quality.
Embodiment
After now specific embodiments of the invention being described in.
Embodiment 1
Get proportion and be 1.157 hydrochloric acid pickling waste liquor 347.1g (300mL) in reactor, under the normal pressure, stir and certain temperature (60～75 ℃) condition under quantitatively add 7.7g sodium chlorate oxygenant in batches.Add the 20.0g calcium aluminate powder then, stirring reaction 1.5～2.5 hours.Last filtered while hot adds 7.4g SODIUM PHOSPHATE, MONOBASIC stablizer in filtrate, stirring and dissolving promptly gets Fe
2O
3Percentage composition is 9.30%, Al
2O
3Percentage composition is 2.72%, and basicity is 4.95%, Fe
2+Concentration is lower than 0.1% stable polyiron chloride aluminium.
Embodiment 2
Take by weighing proportion and be 1.157 hydrochloric acid pickling waste liquor 347.1g (300mL) in reactor, under the normal pressure, stir and certain temperature (60～75 ℃) condition under quantitatively add 7.7g sodium chlorate oxygenant in batches.Add the 25.0g calcium aluminate powder then, stirring reaction 1.5～2.5 hours.Last filtered while hot adds 23.4g sodium phosphate stablizer in filtrate, stirring and dissolving promptly gets Fe
2O
3Percentage composition is 7.78%, Al
2O
3Percentage composition is 3.34%, and basicity is 6.44%, Fe
2+Concentration is lower than 0.1% stable polyiron chloride aluminium.
Embodiment 3
Get proportion and be 1.229 hydrochloric acid pickling waste liquor 368.7g (300mL), technical hydrochloric acid 74mL and 15mL distilled water in reactor, under the normal pressure, stir and certain temperature (60～75 ℃) condition under quantitatively add 8.3g sodium chlorate oxygenant in batches.Add the 32.4g calcium aluminate powder then, stirring reaction 1.5～2.5 hours.Last filtered while hot adds 30.6g sodium phosphate stablizer in filtrate, stirring and dissolving promptly gets Fe
2O
3Percentage composition is 7.77%, Al
2O
3Percentage composition is 3.15%, and basicity is 6.17%, Fe
2+Concentration is lower than 0.1% stable polyiron chloride aluminium.
Embodiment 4
Get proportion and be 1.229 hydrochloric acid pickling waste liquor 368.7g (300mL), under the normal pressure, stir and certain temperature (60～75 ℃) condition under quantitatively add 8.3g sodium chlorate oxygenant in batches.Add the 30.0g calcium aluminate powder then, stirring reaction 1.5～2.5 hours.Last filtered while hot adds 5.9g sodium phosphate stablizer in filtrate, stirring and dissolving promptly gets Fe
2O
3Percentage composition is 5.86%, Al
2O
3Percentage composition is 3.59%, and basicity is 7.87%, Fe
2+Concentration is lower than 0.1% stable polyiron chloride aluminium.
Prepared polymerized ferric-aluminum chloride (PFAC) and other coagulating agent see the following form 1 and table 2 to the contrast of COD in the sewage or waste water and turbidity removal effect in the embodiment of the invention.
Table 1 polymerized ferric-aluminum chloride (PFAC) and of the contrast of bodied ferric sulfate (PFS) coagulating agent to COD in the city domestic sewage and turbidity removal effect
Annotate; Raw water turbidity is 45.5NTU, and COD is 184.6mg/L; PFS (Fe
2O
3=15.1%, B=15.8%); PFAC (Fe
2O
3=5.9%, Al
2O
3=3.4%, B=8.0%); Dosage is in oxide compound.B is a basicity.
From result shown in the table 1 as seen, under identical best dosage condition, polymerized ferric-aluminum chloride (PFAC) coagulating agent is better than bodied ferric sulfate (PFS) to COD in the sanitary sewage and turbidity removal effect, and COD and turbidity removal rate can improve 4～15% and 6～13% respectively.
Table 2 polymerized ferric-aluminum chloride (PFAC) and of the contrast of polymerize aluminum chloride (PAC) coagulating agent to COD in the photoresists factory effluent and turbidity removal effect
Annotate: raw water turbidity is 594NTU, and COD is 678.0mg/L; PAC (Al
2O
3=10.9%, B=71.8%); PFAC (Fe
2O
3=5.9%, Al
2O
3=3.4%, B=8.0%).When coagulating, all add 5ppm cationic polyacrylamide (PAM) coagulant aids.B is a basicity.
From result shown in the table 2 as seen, though the polymerized ferric-aluminum chloride coagulant concentration that is added (9.3%, with Fe
2O
3+ Al
2O
3The meter) be lower than the polymerize aluminum chloride coagulant concentration (10.9%, with Al
2O
3Meter), but it is when the equal volume dosage, and polymerized ferric-aluminum chloride (PFAC) coagulating agent is better than polymerize aluminum chloride (PAC) to COD in the photoresists factory effluent and turbidity removal effect, and COD and turbidity removal rate can improve about 6% and 3% respectively.
Claims (1)
1. the preparation method of a polymerized ferric-aluminum chloride composite coagulating agent is characterized in that having following technological process and step:
A. the preparation of raw material: adopting hydrochloric acid pickling waste liquor and calcium aluminate powder is main raw material; Fe in the hydrochloric acid pickling waste liquor
2+Concentration is 75～90g/L; Al in the calcium aluminate powder
2O
3Content is 47～56%;
B. get a certain amount of hydrochloric acid pickling waste liquor and be positioned in the reactor, under 50～80 ℃ of temperature and agitation condition, add the chloric acid saline oxidizing agent in batches, make ferrous ion all be oxidized to ferric ion;
C. be that 0.05～0.10 ratio adds calcium aluminate powder in the mass ratio of calcium aluminate powder and hydrochloric acid pickling waste liquor then, stirring reaction is 1～3 hour under 50～80 ℃ of temperature, aluminium in the material is dissolved in the liquid phase and with iron ion to greatest extent carries out composite polymeric;
D. filtered while hot then, filtrate, and in P/[Fe+Al] ratio of mol ratio=0.05～0.15 adds phosphoric acid salt or biphosphate salt stabilizing agent, the continuation stirring reaction in filtrate; Reaction finishes, and is cooled to room temperature, promptly gets the liquid polymeric ferric-aluminum chloride composite coagulating agent.
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| CNB200710042744XA CN100554177C (en) | 2007-06-26 | 2007-06-26 | A kind of preparation method of polymerized ferric-aluminum chloride composite coagulating agent |
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| CN100554177C true CN100554177C (en) | 2009-10-28 |
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| CN102515320B (en) * | 2011-11-09 | 2013-06-19 | 中蓝连海设计研究院 | Oxidation-coagulation agent |
| CN102910716A (en) * | 2012-08-27 | 2013-02-06 | 浙江大学 | Method for preparing polymeric ferric aluminum by utilizing metal chlorohydric acid pickling waste liquor |
| CN103626272A (en) * | 2012-08-27 | 2014-03-12 | 广西工学院 | Preparation technology of rare earth heteronuclear polymeric aluminum calcium chloride |
| CN103043759B (en) * | 2012-12-14 | 2014-04-16 | 广东工业大学 | Method for preparing polyaluminium ferric chloride flocculating agent by pickling waste liquid and waste aluminium material |
| CN103288197B (en) * | 2013-04-25 | 2014-07-09 | 太仓市新星轻工助剂厂 | Method for preparing Fe-Al-Ca sewage phosphate-removing agent using waste hydrochloric acid washing liquor |
| CN103435107B (en) * | 2013-08-27 | 2015-04-29 | 肇庆领誉环保实业股份有限公司 | Method for producing sludge conditioner by recycling wastes |
| CN103951022A (en) * | 2013-09-03 | 2014-07-30 | 嘉善绿野环保材料厂(普通合伙) | Multielement polyphosphate ferric chloride coagulant and preparation method thereof |
| CN104973671A (en) * | 2015-06-23 | 2015-10-14 | 河北冀泽生物科技有限公司 | Production method for polyferric aluminum chloride |
| CN105152232A (en) * | 2015-07-07 | 2015-12-16 | 陈泽林 | City sewage treatment agent |
| CN105152295A (en) * | 2015-09-10 | 2015-12-16 | 吴建华 | Preparation method of aluminum ferric chloride solution |
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