CN101049978A - Method for preparing polymerized iron chloride by using cinder of sulfur iron ore - Google Patents
Method for preparing polymerized iron chloride by using cinder of sulfur iron ore Download PDFInfo
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- CN101049978A CN101049978A CN 200710057281 CN200710057281A CN101049978A CN 101049978 A CN101049978 A CN 101049978A CN 200710057281 CN200710057281 CN 200710057281 CN 200710057281 A CN200710057281 A CN 200710057281A CN 101049978 A CN101049978 A CN 101049978A
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Abstract
This invention discloses a method for preparing poly (ferric chloride) from burnt troilite slag. The method comprises: (1) mixing burnt troilite slag and 15-30% HCl at a certain ratio, reacting at 60-95 deg.C for 1-4 h, and filtering; (2) dividing the leached solution into two parts; (3) adding NaOH to one part, and aerating to obtain Fe(OH)3 colloid; (4) adding an appropriate amount of oxidant to the other part, adding composite phosphate as the stabilizer, stirring vigorously, adding the Fe(OH)3 colloid, and aging for 1 h to obtain poly(ferric chloride) product. The method has such advantages as high ecological safety, high product stability and good flocculation effect.
Description
Technical field
The present invention relates to the utilization of resources and environmental protection field, specifically a kind of method that adopts pyrite cinder to prepare poly-ferric chloride.
Background technology
Along with the growing tension of water globe resource, people have also proposed requirements at the higher level to the utilization again of water cycle.In feedwater and wastewater treatment process, it is particularly outstanding that the superiority of flocculation technique seems.Flocculation agent is one of key link of flocculation technique, can be divided into inorganic and organic floculant two big classes by its chemical property.Organic floculant such as polyacrylamide have the good treatment effect to trade effluent, but it costs an arm and a leg, and have necessarily residually in tap water, may exert an influence to human body.Inorganic flocculating agent commonly used has Tai-Ace S 150, aluminum chloride, iron(ic) chloride, ferrous sulfate and various polymerized form thereof.For now, the sedimentation speed of traditional inorganic flocculating agent is slow, and flocculating effect is poor, and cost is higher; Though and the high molecular polymerization flocculation agent is better than traditional flocculation agent treatment effect, the flco volume of formation is big and solid, and the most raw material anxiety of existing preparation method, cost are higher.Therefore, seeking a kind of flocculation agent efficient and with low cost is a very instant task.
Pyrite cinder is to utilize sulfurous iron ore to produce the industrial residue of discharging in the vitriolic process.China is gas washing in SA production big country, and output occupies the third place in the world, wherein account for about 80% with pyrite-based sulfuric acid production, and every production 1t sulfuric acid can produce 0.8～0.9t burning slag, and the whole nation will have an appointment 7 * 10 every year at present
6T waste residue amount.A large amount of burning slags is land occupation not only, and causes soil by the migration conversion, and big G﹠W pollutes.In addition, pyrite cinder is a kind of secondary resource.In order to improve resource utilization; the protection environment is turned harm into good, and some researchs has been carried out in slag roasting utilization both at home and abroad; as brickmaking and cement additire, select briquetting ironmaking behind the slag, extract non-ferrous metal and precious metal etc., but all exist slag utilization and the lower problem of utilization ratio of burning.Adopting pyrite cinder to prepare efficient water conditioner is the most promising one of the method for utilizing of pyrite cinder.
Poly-ferric chloride is a kind of inorganic polymer coagulant, since the eighties in 20th century is synthetic in Japan, be subjected to people's attention with its good application, not only have safe lifeless matter toxicity, and have the alumen ustum of formation big, advantage such as structure is closely knit, consumption is few, sedimentation is fast, dewatering performance of sludge is good.Especially have superiority for processing low temperature, low turbidity water.Significant turbidity removal, oil removing, decolorizing effect are all arranged in the processing of domestic water, process water, municipal wastewater, trade effluent and petroleum waste water, the ability that reduces COD is also arranged, so wide market application prospect is arranged.
Have some at present and prepare the method for poly-ferric chloride, as in high density chlorination ferrous solution, progressively add the alkaline dilute solution or add the weak base solid, [alkalization method prepares the stability and the form distribution research of poly ferric chloride flocculant agent to make the polymerization of ferrous solution generation intense hydrolysis, journal of Zhejiang university, 2003,30 (4): 449～453; The preparation of high dense poly-ferric chloride coagulant and coagulation effect research thereof, Treatment of Industrial Water, 2002,22 (8): 22～25].Though these method technologies are simple, all adopt pure reagent, cost is higher.The method that adopts hydrochloric acid pickling waste liquor to produce poly-ferric chloride is also arranged, as being raw material with the hydrochloric acid pickling waste liquor, adopt the Sodium Nitrite catalyzed oxidation, hydrolysis, the polymerisation step legal system is equipped with successful poly-ferric chloride and [produces poly-ferric chloride with hydrochloric acid pickler, Treatment of Industrial Water, 1997,17 (6): 18～20], but this method production cost height, long reaction time, (basicity was greater than 4 o'clock for the product instability, deposit less than a week separating out precipitation), and remain in nitrite in the water body to the toxic effect of biology.
Summary of the invention
The object of the present invention is to provide a kind of method for preparing poly-ferric chloride with pyrite cinder, this method is less investment not only, and instant effect does not produce secondary pollution, solved pyrite cinder and be deposited in the pollution problem that causes in the environment, made water conditioner product simultaneously with high added value.
Employing pyrite cinder disclosed by the invention prepares the method for poly-ferric chloride, it is characterized in that: with pyrite cinder, hydrochloric acid and sodium hydroxide is raw material, as follows preparation:
1) hydrochloric acid of pyrite cinder and 15%～30% concentration is pressed mass ratio mixed in 0.3: 1～0.6: 1, react 1～4h down at 60～95 ℃, filtration obtains leach liquor, and leach liquor is divided into A and B two portions, and leach liquor A and leach liquor B volume ratio scope are 1: 3～1: 8;
2) add the sodium hydroxide of 10%～30% concentration in leach liquor A, the volume ratio scope of sodium hydroxide and leach liquor A is 0.5: 1～2: 1, generates ferrous hydroxide and ironic hydroxide, and aeration 12～24h makes ferrous hydroxide be converted into ferric hydroxide colloid;
3) in leach liquor B, add oxygenant, the volume ratio scope of oxygenant and leach liquor B is 0.04: 1～0.36: 1, ferrous ion is oxidized to ferric ion, the back adds the stablizer composite phosphate, the quality of the composite phosphate that adds is 1%～4% of a leach liquor total mass, again under vigorous stirring with step 2) ferric hydroxide colloid of preparation adds wherein, slaking 1h promptly gets the poly-ferric chloride product.
The poly-ferric chloride product that the present invention produced is brown solution, density 〉=1.35g/ml, Fe
3+〉=11%, Fe
2+＜0.1%, basicity is 8%～25%.
The present invention has the following advantages:
1. turn waste into wealth resource reutilization.The main raw material of preparation poly-ferric chloride is a pyrite cinder, approximately produces 7 * 10 in China at present
6The t pyrite cinder, hydrochloric acid can adopt technical hydrochloric acid or waste liquid, and this method has been followed circular economy concept, has promptly eliminated the pollution that pyrite cinder is stacked, and has prepared efficient water conditioner again, has reached the purpose of " waste recycling ".
2. production cost is low.This method is raw materials used cheap.On the other hand, this method adds sodium hydroxide with the part in the leach liquor, generates ferrous hydroxide and ironic hydroxide, ferrous hydroxide is easy to be converted into ironic hydroxide in air, aeration makes ferrous hydroxide be converted into ironic hydroxide, can save the oxygenant consumption.
3. ecological security height, non-secondary pollution.The use of aluminum salt flocculant can cause in the water aluminum ion residual too high, and animal, plant, microorganism and the mankind are worked the mischief.And poly-ferric chloride does not have genotoxic potential, and can not produce secondary pollution.
4. flocculating effect is good.The flocculation performance of the poly-ferric chloride product of being produced is better, compare flocculating effect with bodied ferric sulfate and want high by 10～30%, and alumen ustum is closely knit, and the sedimentation sludge volume is little.
Embodiment
The present invention is a raw material with pyrite cinder, hydrochloric acid and sodium hydroxide, preparation as follows: the mass ratio that the hydrochloric acid of pyrite cinder and 20%～30% was pressed 0.35: 1～0.5: 1 mixes, react 1～3h down at 70～95 ℃, filtration obtains leach liquor, with leach liquor separated into two parts A and B, the ratio of leach liquor A and leach liquor B is 1: 3～1: 6; Add sodium hydroxide or ammoniacal liquor generation ferrous hydroxide and ironic hydroxide in leach liquor A, aeration makes ferrous hydroxide be converted into ferric hydroxide colloid; In leach liquor B, add oxygenant 30% concentration hydrogen peroxide or clorox, the volume ratio scope of oxygenant and leach liquor B is 0.04: 1～0.36: 1, ferrous ion is oxidized to ferric ion, 1～4% the composite phosphate that adds quality again and be the leach liquor total mass is as stablizer, under vigorous stirring, to be added wherein by the ferric hydroxide colloid of leach liquor A preparation, slaking 1h promptly gets the poly-ferric chloride product.
The top condition of reaction is: concentration of hydrochloric acid is 25～30%, and the mass ratio of pyrite cinder and hydrochloric acid is 0.35: 1～0.45: 1; Temperature of reaction is 85～95 ℃, and the reaction times is 1～1.5h; The ratio of leach liquor A and B is 1: 5～1: 6; Adding concentration sodium hydroxide is 15%～30%; Sodium hydroxide that adds and the volume ratio of leach liquor A are 1: 1～2: 1; The oxygenant that adopts can be 10～30% hydrogen peroxide or clorox, the oxygenant of adding and leach liquor B volume ratio scope 0.05: 1～0.3: 1; The amount of the best of composite phosphate is 1.5～3.0% of a leach liquor total mass.
The present invention is described in more detail below by embodiment.
Embodiment 1
With pyrite cinder, hydrochloric acid and sodium hydroxide is raw material, as follows preparation:
1) by 0.4: 1 mass ratio, with the mixed in hydrochloric acid of 100g pyrite cinder and 218ml 28%, react 2h down at 80 ℃, filter and obtain the 160ml leach liquor, with leach liquor separated into two parts A and B, the volume ratio of A and B is 1: 6.
2) 1: 1 by volume, in A, add 25% sodium hydroxide and generate ferrous hydroxide and ironic hydroxide, aeration 15h makes ferrous hydroxide be converted into ferric hydroxide colloid.
3) 0.07: 1 by volume, the hydrogen peroxide that adds oxygenant 30% concentration in B is oxidized to ferric ion with ferrous ion, add the compound phosphoric acid salt stabilizing agent, quality is 3% of a leach liquor total mass, under vigorous stirring, with 2) ferric hydroxide colloid of preparation adds wherein, and slaking 1h promptly gets the poly-ferric chloride product.
Embodiment 2
With pyrite cinder, hydrochloric acid and sodium hydroxide is raw material, as follows preparation:
1) by 0.45: 1 mass ratio, with the mixed in hydrochloric acid of 100g pyrite cinder and 193ml 30%, react 1h down at 95 ℃, filter and obtain the 140ml leach liquor, with leach liquor separated into two parts A and B, the volume ratio of A and B is 1: 6.
2) 1: 1 by volume, the sodium hydroxide that adds 20ml 30% in A generated ferrous hydroxide and ironic hydroxide, and aeration 12h makes ferrous hydroxide be converted into ferric hydroxide colloid.
3) 0.15: 1 by volume, the hydrogen peroxide that adds oxygenant 15% concentration in B is oxidized to ferric ion with ferrous ion, add the compound phosphoric acid salt stabilizing agent, quality is 2% of a leach liquor total mass, under vigorous stirring, freshly prepd ferric hydroxide colloid is added wherein, and slaking 1h promptly gets the poly-ferric chloride product.
Embodiment 3
With pyrite cinder, hydrochloric acid and sodium hydroxide is raw material, as follows preparation:
1) by 0.35: 1 mass ratio, with the mixed in hydrochloric acid of 100g pyrite cinder and 255ml 24%, react 1.5h down at 85 ℃, filter and obtain the 210ml leach liquor, with leach liquor separated into two parts A and B, the volume ratio of A and B is 1: 5.
2) 1: 1 by volume, the sodium hydroxide that adds 35ml 28% in A generated ferrous hydroxide and ironic hydroxide, and aeration 24h makes ferrous hydroxide be converted into ferric hydroxide colloid.
3) 0.075: 1 by volume, the hydrogen peroxide that adds oxygenant 30% concentration in B is oxidized to ferric ion with ferrous ion, add the compound phosphoric acid salt stabilizing agent, quality is 2.4% of a leach liquor total mass, under vigorous stirring, freshly prepd ferric hydroxide colloid is added wherein, and slaking 1h promptly gets the poly-ferric chloride product.
Claims (9)
1. method that adopts pyrite cinder to prepare poly-ferric chloride, it is characterized in that: with pyrite cinder, hydrochloric acid and sodium hydroxide is raw material, as follows preparation:
1) hydrochloric acid of pyrite cinder and 15%～30% concentration is pressed mass ratio mixed in 0.3: 1～0.6: 1, react 1～4h down at 60～95 ℃, filtration obtains leach liquor, and leach liquor is divided into A and B two portions, and leach liquor A and leach liquor B volume ratio scope are 1: 3～1: 8;
2) add the sodium hydroxide of 10%～30% concentration in leach liquor A, the volume ratio scope of sodium hydroxide and leach liquor A is 0.5: 1～2: 1, generates ferrous hydroxide and ironic hydroxide, and aeration 12～24h makes ferrous hydroxide be converted into ferric hydroxide colloid;
3) in leach liquor B, add oxygenant, the volume ratio scope of oxygenant and leach liquor B is 0.04: 1～0.36: 1, ferrous ion is oxidized to ferric ion, the back adds the stablizer composite phosphate, the quality of the composite phosphate that adds is 1%～4% of a leach liquor total mass, again under vigorous stirring with step 2) ferric hydroxide colloid of preparation adds wherein, slaking 1h promptly gets the poly-ferric chloride product.
2. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the used salt acid concentration is 25%～30%.
3. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the mass ratio of used pyrite cinder and hydrochloric acid is 0.35: 1～0.45: 1.
4. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the temperature of reaction of hydrochloric acid and pyrite cinder is 85～95 ℃.
5. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the reaction times of hydrochloric acid and pyrite cinder is 1～1.5h.
6. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the ratio of leach liquor A and leach liquor B is 1: 5～1: 6.
7. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: adding concentration sodium hydroxide is 15%～30%, and the volume ratio of the sodium hydroxide of adding and leach liquor A is 1: 1～2: 1.
8. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the oxygenant that is adopted is 10～30% concentration hydrogen peroxide, and oxygenant and leach liquor B volume ratio scope are: 0.05: 1～0.3: 1.
9. prepare the method for poly-ferric chloride according to the described pyrite cinder of claim 1, it is characterized in that: the quality of the composite phosphate of adding is 1.5～3.0% of a leach liquor total mass.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200710057281 CN101049978A (en) | 2007-04-30 | 2007-04-30 | Method for preparing polymerized iron chloride by using cinder of sulfur iron ore |
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|---|---|---|---|
| CN 200710057281 CN101049978A (en) | 2007-04-30 | 2007-04-30 | Method for preparing polymerized iron chloride by using cinder of sulfur iron ore |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725869A (en) * | 2013-12-24 | 2014-04-16 | 师兆忠 | Technique for preparing iron concentrate from pyrite cinder by nitric acid-hydrochloric acid combined treatment |
| CN103755003A (en) * | 2014-01-13 | 2014-04-30 | 大连理工大学 | Synthetic method of composite molybdenum removing agent and method for removing molybdenum |
| CN105984893A (en) * | 2015-02-07 | 2016-10-05 | 耿兆翔 | Pyrite cinder separation, recovery and recycling method |
| CN111498912A (en) * | 2020-05-14 | 2020-08-07 | 河南佰利联新材料有限公司 | Resource utilization method of waste acid water produced by chlorination process |
| CN113968610A (en) * | 2021-09-22 | 2022-01-25 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
-
2007
- 2007-04-30 CN CN 200710057281 patent/CN101049978A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103725869A (en) * | 2013-12-24 | 2014-04-16 | 师兆忠 | Technique for preparing iron concentrate from pyrite cinder by nitric acid-hydrochloric acid combined treatment |
| CN103755003A (en) * | 2014-01-13 | 2014-04-30 | 大连理工大学 | Synthetic method of composite molybdenum removing agent and method for removing molybdenum |
| CN105984893A (en) * | 2015-02-07 | 2016-10-05 | 耿兆翔 | Pyrite cinder separation, recovery and recycling method |
| CN111498912A (en) * | 2020-05-14 | 2020-08-07 | 河南佰利联新材料有限公司 | Resource utilization method of waste acid water produced by chlorination process |
| CN113968610A (en) * | 2021-09-22 | 2022-01-25 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
| CN113968610B (en) * | 2021-09-22 | 2022-03-15 | 赛恩斯环保股份有限公司 | Method for preparing biological flocculant by using biological iron-calcium slag in biological heap leaching |
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