CN104495995A - Method for preparing polyaluminum ferric chloride sulfate by using industrial waste - Google Patents
Method for preparing polyaluminum ferric chloride sulfate by using industrial waste Download PDFInfo
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- CN104495995A CN104495995A CN201410779630.3A CN201410779630A CN104495995A CN 104495995 A CN104495995 A CN 104495995A CN 201410779630 A CN201410779630 A CN 201410779630A CN 104495995 A CN104495995 A CN 104495995A
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- ferric chloride
- poly
- chloride sulfate
- aluminum ferric
- aluminum
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
- C02F1/5245—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents using basic salts, e.g. of aluminium and iron
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
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- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a method for preparing polyaluminum ferric chloride sulfate by using industrial waste. The method comprises the following steps: mixing industrial byproducts waste hydrochloric acid, aluminum-containing sludge and sulfuric acid in a certain proportion, stirring till the aluminum-containing sludge is fully dissolved, insulating and stirring at normal temperature to react to obtain a polyaluminum ferric chloride sulfate semi-product; and inputting ferric chloride and calcium aluminate powder, fully stirring till the ferric chloride and calcium aluminate powder are fully dissolved, inputting a synergist, insulating and stirring at normal temperature to react, and cooling to obtain a finished product polyaluminum ferric chloride sulfate. The method provided by the invention has the beneficial effects that by using the industrial byproducts waste hydrochloric acid and aluminum-containing sludge, the cost is lowered and the treatment cost of treating waste acid and aluminum-containing sludge is further avoided, so that the target of treatment of a waste with another waste is achieved; by controlling a reasonable aluminum and iron proportion design and preparing an efficient water purifier polyaluminum ferric chloride sulfate, the finished product is stable in property and few in insoluble substance and is good in flocculation effect and large in alumen ustum for treating sewage. The removal rates on COD and turbidity in sewage are superior to those of other similar products.
Description
Technical field
The present invention relates to a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate.
Background technology
At present, the environmental problem that expanding economy causes has become the problem demanding prompt solution of China, wherein solves the water resources crisis most important thing especially.Coagulating sedimentation, as one of key technique in sewage treatment process, plays irreplaceable effect to the effluent quality of whole technical process and running cost.The most widely used coagulating agent of current China is aluminium salt and molysite, wherein to have dosage little for polymerize aluminum chloride (PAC), on water body on water pH value impact little, what alumen ustum formation speed was fast, suitable adds the series of advantages such as scope is wide, but its flco throw out intensity produced is little, granularity is little, cause dehydration property poor, when water temperature is low, coagulation effect is undesirable; Coagulant polymeric ferric sulfate (PFS) hydrolysis rate of another kind of widespread use is fast, and alumen ustum formation speed is fast, the fine and close consolidation of flco, and dehydration property is good, can play flocculation sediment effect preferably when water temperature is lower.But be greater than finite concentration when making treatment of Organic Wastewater, the part iron in PFS can form metallorganics and soluble in water, make water outlet show light brown, cause effluent color dilution not up to standard, and free state iron ion can cause secondary pollution.
Compare traditional flocculant PAC and PFS, poly-aluminum ferric chloride sulfate (PAFSC) is as a kind of new type compound inorganic flocculating agent, and it has the advantage that aluminium salt purifying water effect is superior and molysite settling velocity is fast concurrently.Different kinds of ions is comprised as Al in the aggressiveness of poly-aluminum ferric chloride sulfate (PAFSC)
3+, Fe
3+, SO
4 2-, Cl
-, structure and the absorption property of often kind of ion pair throw out aggressiveness can produce different effects, and the joint contribution of different kinds of ions improves the stability of flocculating effect and product.CN200910112803.5 uses iron content bauxite trihydrate, hydrochloric acid and sulfuric acid to prepare poly-aluminum ferric chloride sulfate, coreaction 5 ~ 9h at 90 ~ 100 DEG C, and the preparation cost of its finished product and energy consumption are relatively high; And CN200910196018.2 adopts the raw material such as ferrous sulfate, hydrochloric acid and hydrogen peroxide to prepare double-acid ferro-aluminum, its preparation technology's relative complex, and due to the control of its reaction times and temperature, make finished product basicity little, the polymerization degree is low, affects its flocculating effect.This patent adopts industrial by-product hydrochloric acid, aluminium-containing sludge prepares double-acid ferro-aluminum, and its technique is simple, and with low cost, basicity is high, and at present, the achievement preparing poly-aluminum ferric chloride sulfate in this approach has no report.
Summary of the invention
The technical problem to be solved in the present invention is: based on the problems referred to above, the invention provides a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate, obtained product is good for flocculating effect during sewage disposal, alumen ustum large, is all better than like product to the clearance of COD in sewage and turbidity.
The present invention solves the technical scheme that its technical problem adopts: a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate, comprises the following steps:
(1) industrial by-product waste hydrochloric acid, aluminium-containing sludge, sulfuric acid are mixed by a certain percentage, drop into reactor, be stirred to aluminium-containing sludge and all dissolve, 45 ~ 55 DEG C of normal pressure heat-insulating stirring reaction 0.2 ~ 0.5h, leave standstill 0.5h, obtain poly-aluminum ferric chloride sulfate work in-process;
(2) iron(ic) chloride, calcium aluminate powder is added in the poly-aluminum ferric chloride sulfate work in-process obtained to step (1), calcium aluminate powder meets water heat release makes mixed solution be warming up to 80 ~ 85 DEG C, abundant stirring is all dissolved, continue to be heated to 90 ~ 105 DEG C, add synergistic agent, normal pressure heat-insulating stirring reaction 1 ~ 2h, cooling obtains finished product poly-aluminum ferric chloride sulfate.
Further, in step (1), the acidity of industrial by-product waste hydrochloric acid counts 10 ~ 35% with HCl, refers to the weight percent of HCl in HCl.
Further, in step (1), aluminium-containing sludge comprises Al (OH)
3, its aluminium content is with Al
2o
3count 6 ~ 40%, with Al
2o
3meter refers to Al
2o
3weight percent.
Further, in step (1), the blending ratio of hydrochloric acid, aluminium-containing sludge and sulfuric acid presses aluminium content, acidity, HCl and H in poly-aluminum ferric chloride sulfate work in-process
2sO
4mass ratio calculate.
Further, in poly-aluminum ferric chloride sulfate work in-process aluminium content with Al
2o
3count 4 ~ 5%, the half-finished acidity of poly-aluminum ferric chloride sulfate counts 0.8 ~ 2% with HCl, HCl and H in poly-aluminum ferric chloride sulfate work in-process
2sO
4mass ratio be 5:1 ~ 7:1.
Further, in step (2), synergistic agent is that metasilicic acid is received or trolamine, and its addition is that step (1) and step (2) add 0.1 ~ 3% of material total amount.
Further, the aluminium content of the middle finished product poly-aluminum ferric chloride sulfate of step (2) is with Al
2o
3meter ﹥ 10%, all iron content is with Fe
2o
3count 1 ~ 3%, basicity is 70 ~ 85%, and insolubles ﹤ 1%, with Fe
2o
3meter refers to Fe
2o
3weight percent.
The invention has the beneficial effects as follows: utilize industrial by-product waste hydrochloric acid and aluminium-containing sludge, the cost-saving processing costs removing again process spent acid and aluminium-containing sludge from, reaches the target of the treatment of wastes with processes of wastes against one another; By controlling rational ferro-aluminum Proportionality design and preparing efficient water-purifying agent poly-aluminum ferric chloride sulfate, end product properties is stablized, and insolubles is few, and, alumen ustum good for flocculating effect during sewage disposal is large, is all better than other like products to the clearance of COD in sewage and turbidity.
Embodiment
The invention will be further described in conjunction with specific embodiments now, and following examples are intended to the present invention instead of limitation of the invention further are described.
Embodiment one
Be that the industrial by-product waste hydrochloric acid 80 kilograms of 31.19%, aluminium content are (with Al by concentration
2o
3meter) be 24.60% aluminium-containing sludge 50 kilograms, concentration be 98% 4 kilograms, sulfuric acid, be uniformly mixed in water 100 kilograms of input reactors, when being warmed up to 45 DEG C, normal pressure heat-insulating stirring reaction 0.2h.Leave standstill 0.5h, the thin slag in bottom of draining, gets supernatant liquor and obtains work in-process aluminum chloride and Tai-Ace S 150 mixture.Then in reactor, all iron content is added (with Fe
2o
3meter) be 15.34%, salt acidacidity be 2.68% iron(ic) chloride raw material 50 kilograms and aluminium content (with Al
2o
3meter) be 51.97%, the calcium aluminate powder of calcium oxide 35.45% 40 kilograms to be to regulate basicity, abundant stirring, calcium aluminate powder meets water heat release can make mixed solution be warming up to 80 DEG C, add the Starso 3.5 kilograms of 30% as stablizer, continue to be heated to 105 DEG C, while stirring, normal pressure heat-insulating reaction 1h, cools to obtain finished product PAFSC.Finished product PAFSC aluminium content is (with Al
2o
3meter) be 10.10%, all iron content is (with Fe
2o
3meter) be 2.34%, basicity is 74.74%, insolubles <1%.
Embodiment two
Be that the industrial by-product waste hydrochloric acid 180 kilograms of 15.69%, aluminium content are (with Al by concentration
2o
3meter) be 18.69% aluminium-containing sludge 70 kilograms, concentration be uniformly mixed in sulfuric acid 4.8 kilograms of input reactors of 98%, when being warmed up to 50 DEG C, normal pressure heat-insulating stirring reaction 0.5h.Leave standstill 0.5h, the thin slag in bottom of draining, gets supernatant liquor and obtains work in-process aluminum chloride and Tai-Ace S 150 mixture.Then in reactor, all iron content is added (with Fe
2o
3meter) be 15.34%, salt acidacidity be 2.68% iron(ic) chloride raw material 50 kilograms and aluminium content (with Al
2o
3meter) be 51.97%, calcium oxide is that the calcium aluminate powder 50 kilograms of 35.45% is to regulate basicity, abundant stirring, calcium aluminate powder meets water heat release can make mixed solution be warming up to 85 DEG C, add the trolamine 3.5 kilograms of 30% as stablizer, continue to be heated to 100 DEG C, while stirring, normal pressure heat-insulating reaction 1.5h, cools to obtain finished product PAFSC.Finished product PAFSC aluminium content is (with Al
2o
3meter) be 10.9%, all iron content is (with Fe
2o
3meter) be 2.14%, basicity is 78.97%, insolubles <1%.
Embodiment three
Be that the industrial by-product waste hydrochloric acid 140 kilograms of 18.30%, aluminium content are (with Al by concentration
2o
3meter) be 10.9% aluminium-containing sludge 115 kilograms, concentration be uniformly mixed in sulfuric acid 5.2 kilograms of input reactors of 98%, when being warmed up to 55 DEG C, normal pressure heat-insulating stirring reaction 0.3h.Leave standstill 0.5h, the thin slag in bottom of draining, gets supernatant liquor and obtains work in-process aluminum chloride and Tai-Ace S 150 mixture.Then in reactor, all iron content is added (with Fe
2o
3meter) be 15.34%, salt acidacidity be 2.68% iron(ic) chloride raw material 50 kilograms and aluminium content (with Al
2o
3meter) be 51.97%, calcium oxide is that the calcium aluminate powder 45 kilograms of 35.45% is to regulate basicity, abundant stirring, calcium aluminate powder meets water heat release can make mixed solution be warming up to 82 DEG C, add the Starso 3.5 kilograms of 30% as stablizer, continue to be heated to 90 DEG C, while stirring, normal pressure heat-insulating reaction 2h, cools to obtain finished product PAFSC.Finished product PAFSC aluminium content is (with Al
2o
3meter) 10.01%, all iron content is (with Fe
2o
3meter) be 2.14%, basicity is 77.34%, insolubles <1%.
Poly-aluminum ferric chloride sulfate effect evaluation method of the present invention:
1, water test sinks in certain sewage work two
Sewage source sinks water for certain sewage work two, its COD is 103.5mg/L, get the polymerize aluminum chloride (PAC) of identical dosage amount, aluminium iron polychloride (PAFC), PAFS (PACX-2) and finished product poly-aluminum ferric chloride sulfate (PAFSC) respectively to add in two heavy water as flocculation agent, compare COD removal level.The results are shown in Table 1.
The different flocculation agent of table 1 sinks the COD clearance of water to certain sewage work two
2, the former water test of certain sewage work
For investigating poly-aluminum ferric chloride sulfate to the treatment effect of high organic loading sewage, getting the former water of certain sewage work is sample, and its COD is 431.9mg/L, and turbidity is 404.34NTU.Flocculation agent adopts PAC, PAFC, PACX-2 and PAFSC respectively, and dosage is 2 ‰, the results are shown in Table 2.
The different flocculation agent of table 2 is to the result of the former water of certain sewage work
Conclusion: compare other like products, the sewage of PAFSC to the sewage of low COD or high COD all has higher clearance, especially when high COD sewage process, PAFSC all has more superior treatment effect to COD of sewage and turbidity removal rate, and the sewage of PAFSC process, the fine and close consolidation of flco, follow-up sludge dewatering is effective.
With above-mentioned according to desirable embodiment of the present invention for enlightenment, by above-mentioned description, relevant staff in the scope not departing from this invention technological thought, can carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to right.
Claims (7)
1. utilize industrial waste to prepare a method for poly-aluminum ferric chloride sulfate, it is characterized in that: comprise the following steps:
(1) industrial by-product waste hydrochloric acid, aluminium-containing sludge, sulfuric acid are mixed by a certain percentage, drop into reactor, be stirred to aluminium-containing sludge and all dissolve, 45 ~ 55 DEG C of normal pressure heat-insulating stirring reaction 0.2 ~ 0.5h, leave standstill 0.5h, obtain poly-aluminum ferric chloride sulfate work in-process;
(2) iron(ic) chloride, calcium aluminate powder is added in the poly-aluminum ferric chloride sulfate work in-process obtained to step (1), calcium aluminate powder meets water heat release makes mixed solution be warming up to 80 ~ 85 DEG C, abundant stirring is all dissolved, continue to be heated to 90 ~ 105 DEG C, add synergistic agent, normal pressure heat-insulating stirring reaction 1 ~ 2h, cooling obtains finished product poly-aluminum ferric chloride sulfate.
2. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 1, is characterized in that: in described step (1), the acidity of industrial by-product waste hydrochloric acid counts 10 ~ 35% with HCl.
3. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 1, is characterized in that: in described step (1), aluminium-containing sludge comprises Al (OH)
3, its aluminium content is with Al
2o
3count 6 ~ 40%.
4. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 1, is characterized in that: in described step (1), the blending ratio of hydrochloric acid, aluminium-containing sludge and sulfuric acid is by aluminium content, acidity, HCl and H in poly-aluminum ferric chloride sulfate work in-process
2sO
4mass ratio calculate.
5. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 4, is characterized in that: in described poly-aluminum ferric chloride sulfate work in-process, aluminium content is with Al
2o
3count 4 ~ 5%, the half-finished acidity of poly-aluminum ferric chloride sulfate counts 0.8 ~ 2% with HCl, HCl and H in poly-aluminum ferric chloride sulfate work in-process
2sO
4mass ratio be 5:1 ~ 7:1.
6. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 1, it is characterized in that: in described step (2), synergistic agent is that metasilicic acid is received or trolamine, and its addition is that step (1) and step (2) add 0.1 ~ 3% of material total amount.
7. a kind of method utilizing industrial waste to prepare poly-aluminum ferric chloride sulfate according to claim 1, is characterized in that: in described step (2), the aluminium content of finished product poly-aluminum ferric chloride sulfate is with Al
2o
3count ﹥ 10%, all iron content is with Fe
2o
3count 1 ~ 3%, basicity is 70 ~ 85%, insolubles ﹤ 1%.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105621524A (en) * | 2016-04-06 | 2016-06-01 | 杭州大业环保科技有限公司 | Environment-friendly sewage treatment agent and preparation method thereof |
| CN105645536A (en) * | 2016-01-05 | 2016-06-08 | 付春平 | Composite water-treatment coagulant prepared from high-iron gibbsite and preparation method thereof |
| CN107879518A (en) * | 2017-12-15 | 2018-04-06 | 周鼎力 | A kind of purification apparatus of drag-out |
| CN108147468A (en) * | 2018-01-24 | 2018-06-12 | 金学芳 | The method for preparing Polyaluminium Sulfate Chloride iron using by-product aluminum sulfate and by-product dust technology |
| CN110540280A (en) * | 2019-10-12 | 2019-12-06 | 广东华锋碧江环保科技有限公司 | Water purifying agent and preparation method thereof |
| CN111003772A (en) * | 2019-12-13 | 2020-04-14 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105645536A (en) * | 2016-01-05 | 2016-06-08 | 付春平 | Composite water-treatment coagulant prepared from high-iron gibbsite and preparation method thereof |
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| CN107879518A (en) * | 2017-12-15 | 2018-04-06 | 周鼎力 | A kind of purification apparatus of drag-out |
| CN108147468A (en) * | 2018-01-24 | 2018-06-12 | 金学芳 | The method for preparing Polyaluminium Sulfate Chloride iron using by-product aluminum sulfate and by-product dust technology |
| CN110540280A (en) * | 2019-10-12 | 2019-12-06 | 广东华锋碧江环保科技有限公司 | Water purifying agent and preparation method thereof |
| CN111003772A (en) * | 2019-12-13 | 2020-04-14 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
| CN111003772B (en) * | 2019-12-13 | 2022-08-23 | 杭州萧山三江净水剂有限公司 | Preparation method of dephosphorization polymeric aluminum iron and closed reaction kettle for preparation |
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Application publication date: 20150408 |