CN104761002B - A preparing process of energy-saving environmental-friendly type modified polymeric ferric sulfate - Google Patents
A preparing process of energy-saving environmental-friendly type modified polymeric ferric sulfate Download PDFInfo
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Abstract
The invention relates to a preparing process of energy-saving environmental-friendly type modified polymeric ferric sulfate. The process includes following steps: adding polyaluminum chloride waste slag and a sulfuric acid type ferrous sulfate-acid mixture into a pretreatment kettle, heating, stirring, reacting and performing filter pressing to obtain a first reaction liquid material; adding green vitriol and a sulfuric acid type ferrous sulfate-acid mixture into a pretreatment kettle and stirring to obtain a second reaction liquid material; and adding the first and second reaction liquid materials into a sealed acid-resistant pressure-resistant reactor, adding a catalyst solution and a cocatalyst solution, feeding oxygen, heating, reacting, and cooling to obtain a modified polymeric ferric sulfate solution. The beneficial effects of the process are that the polymeric ferric sulfate containing a trace amount of aluminum and silicon is high in added value, has flocculation effects superior to flocculation effects of polymeric ferric sulfate, and can be used for treatment of high-turbidity high-COD printing and dying waste water; production raw materials are all industrial waste materials; the raw material cost is reduced; reaction time is shortened; and the time cost is saved.
Description
Technical field
The present invention relates to a kind of preparation technology of energy saving and environment friendly improved PFS.
Background technology
Molysite and aluminium salt are net as two the most frequently used classes of sewage-treating agent in the market as traditional inorganic flocculating agent
Water material.And bodied ferric sulfate (PFS) and poly-ferric chloride obtain the product of practical application to have developed Ferric Salt Flocculants at present
It is bodied ferric sulfate.When bodied ferric sulfate is used for coagulating treatment, because its solubility product constant is small, hydrolysis rate is fast, and flco is intensive
And quality is big, dehydration property is good, suitable water body pH wide ranges, decolouring for industrial wastewaters such as printing and dyeing, papermaking, imitates except COD
Fruit is preferably.But, bodied ferric sulfate is acid relatively strong, and supernatant yellowing is frequently accompanied by with corrosivity, and during its treatment waste water
Phenomenon, influences effluent color dilution, therefore limit it and use.
At present, the industrialization production method of PFS is mainly two kinds, and one kind is oxidizing method, using sodium chlorate, secondary chlorine
The oxidizing sulfuric acid type such as sour sodium or hydrogen peroxide is ferrous, suitable control ferrous sulfate and sulfuric acid ratio, with prepare iron content and
Basicity meets the product of GB 14591-93.Second is catalytic oxidation, that is, it is catalyst to use natrium nitrosum, is passed through oxygen
Gas is by sulfuric acid type ferrous oxidation into hydrolytic polymerization again after ferric sulfate.The advantage of oxidizing method is the short reaction time, oxidation effect
Rate is high, but the expense of raw materials of oxidant is expensive, the oxidant that CN101037234A analysis production bodied ferric sulfates per ton are used into
This is 137 yuan (oxidant is by taking sodium chlorate as an example), and cost of material is too high, is unfavorable for the industrialization production of enterprise.Second method,
I.e. catalytic oxidation, due to its low production cost, has turned into the preferred polyaluminum sulfate process for making iron of enterprise, but be catalyzed at present
The catalyst added in oxidizing process can in the stage of reaction release sour gas such as nitrogen oxides, and the method reaction time compared with
It is long, generally 4~5h, in actual production, in order to ensure the oxygenation efficiency of ferrous iron, its reaction time is 8~10h even longer.
In sum, take and be efficiently modified technique, make PFS flocculating effects more preferable；Optimized production process, clean manufacturing turns into
The Main way of bodied ferric sulfate future development.To solve problem above, prepared by the present invention a kind of energy saving and environment friendly modified poly-
Ferric sulfate is closed, introducing Trace Aluminum, the bodied ferric sulfate added value of silicon are high, and flocculating effect is better than bodied ferric sulfate, can be used for high turbid
The treatment of COD dyeing waste waters high；In production technology, the raw materials for production of bodied ferric sulfate are industrial waste, using catalysis oxidation
Method, eliminates the sodium chlorate of costliness or the expense of the oxidant such as hydrogen peroxide, and economize in raw materials cost, adds co-catalyst and with following
Ring pump strong agitation increased the efficiency of ferrous iron, the reaction time is shorten to 2.5~4h from 8~10h, save the time
Cost, finally, reactor upper gas pipeline connects the sour gas such as alkali liquor absorption tower, the nitrogen oxides that absorbing reaction is produced,
Reduce the discharge of pernicious gas.
The content of the invention
The technical problem to be solved in the present invention is：Based on above mentioned problem, the present invention provides a kind of energy saving and environment friendly modified poly-
The preparation technology for closing ferric sulfate.
The present invention solves a technical scheme being used of its technical problem：A kind of energy saving and environment friendly modified poly sulfuric acid
The preparation technology of iron, comprises the following steps：
(1) by polyaluminium waste slag of aluminum and sulfuric acid type ferrous acid input pretreatment reaction kettle, 45~65 DEG C, stirring are warming up to
0.5~1h of reaction, press filtration must react liquid material one；
(2) by green vitriol and sulfuric acid type ferrous acid input pretreatment reaction kettle, 0.5~1h is stirred under normal temperature, obtains reaction liquid material
Two；
(3) will be during reaction liquid material one and reaction liquid material two put into closed acidproof resistance to compression reactor, open the circulation pump, addition is urged
Agent solution and co-catalyst solution, are passed through oxygen, are warming up to 55~90 DEG C, react 1.5~2h, cool down to obtain modified poly sulfuric acid
Ferrous solution.
Further, polyaluminium chloride residue is production aluminium polychloride finished product bottom residues after press filtration in step (1)
Semi-solid material, polyaluminium chloride residue contains aluminium polychloride and a small amount of silicon, and its aluminium content is with Al2O37~12% are calculated as,
Silicone content is with SiO2It is calculated as 3~7%.
Further, polyaluminium chloride residue and the mass ratio of sulfuric acid type ferrous acid are 1 in step (1)：1.5.
Further, the sulfuric acid type ferrous acid in step (1) and step (2), its iron content is with Fe2O31~18% is calculated as,
Acidity is calculated as 4~25% with sulfuric acid.
Further, in step (2) iron content of green vitriol with Fe2O3It is calculated as 18~30%.
Further, the iron content of liquid material two is reacted in step (2) with Fe2O3It is calculated as 12~18%, basicity is 50~
70%.
Further, the mass ratio that adds of reaction liquid material one and reaction liquid material two is 1 in step (3)：5.
Further, the catalyst in step (3) is natrium nitrosum, and co-catalyst is sodium iodide.
Further, natrium nitrosum and sodium iodide are made into quality by catalyst and co-catalyst when in use in step (3)
Concentration distinguishes 25% and 2% mixed aqueous solution, and dosage is react the mass of liquid material two 1.5~2%.
Further, oxygen intake is excessive in step (3), preferably reacts 1.65~the 3.3 ‰ of liquid material gross mass.
The energy saving and environment friendly improved PFS of finished product is dark brown liquid, and iron content is with Fe2O3% is calculated as 11.5~
16%, aluminium content is with Al2O30.5~0.7% is calculated as, silicone content is with SiO20.2~0.5% is calculated as, basicity is 9~14%, no
Molten thing<0.3%.
The beneficial effects of the invention are as follows：Introduce Trace Aluminum, the bodied ferric sulfate added value of silicon high, flocculating effect is better than polymerization
Ferric sulfate, can be used for the treatment of turbid COD dyeing waste waters high high；In production technology, the raw materials for production of bodied ferric sulfate are industry
Waste material, using catalytic oxidation, eliminates the expense of the oxidants such as the sodium chlorate or hydrogen peroxide of costliness, and economize in raw materials cost,
Add co-catalyst and the efficiency of ferrous iron is increased with circulating pump strong agitation, the reaction time is shortened from 8~10h
It is 2.5~4h, saves time cost, finally, reactor upper gas pipeline connection alkali liquor absorption tower, the nitrogen that absorbing reaction is produced
The sour gas such as oxide, reduce the discharge of pernicious gas.
Specific embodiment
Presently in connection with specific embodiment, the invention will be further described, and following examples are intended to illustrate rather than
Limitation of the invention further.
Embodiment 1
By 30kg polyaluminiums waste slag of aluminum, (aluminium content is with Al2O37% is calculated as, silicone content is with SiO2Be calculated as 3%), 45kg sulphur
(iron content is with Fe for acid type ferrous acid2O34% is calculated as, acidity is calculated as 12%) mixing input pretreatment reaction kettle with sulfuric acid, is warming up to
45~65 DEG C, stirring reaction 0.5h, press filtration obtains 50kg reaction liquid materials one.
By 130kg green vitriols, (iron content is with Fe2O3It is calculated as 20%) that (iron content is with Fe with 120kg sulfuric acid types ferrous acid2O3%
4% is calculated as, acidity is calculated as 12%) putting into pretreatment reaction kettle with sulfuric acid, and 0.5~1h is stirred under normal temperature, obtains 250kg reaction liquid materials
Two.
Will be during reaction liquid material one to put into closed acidproof resistance to compression reactor with reaction liquid material two, open the circulation pump is added
3.75kg mass concentrations are 25% sodium nitrite solution (containing 2% sodium iodide), are passed through oxygen, and oxygen flow is 0.2m3/ h, rises
Temperature reacts 1.5~2h to 55~90 DEG C, cools down to obtain improved PFS solution 300kg.
Embodiment 2
By 60kg polyaluminiums waste slag of aluminum, (aluminium content is with Al2O38% is calculated as, silicone content is with SiO2Be calculated as 4%), 90kg sulphur
(iron content is with Fe for acid type ferrous acid2O35% is calculated as, acidity is calculated as 15%) mixing input pretreatment reaction kettle with sulfuric acid, is warming up to
45~65 DEG C, stirring reaction 1h after press filtration, obtains 100kg reaction liquid materials one.
By 260kg green vitriols, (iron content is with Fe2O3Be calculated as 20%), (iron content is with Fe for 230kg sulfuric acid types ferrous acid2O3It is calculated as
4%, acidity is calculated as 12%) with sulfuric acid and 10kg water puts into pretreatment reaction kettle, and 0.5h is stirred under normal temperature, obtains 500kg reaction solutions
Material two.
Will be during reaction liquid material one to put into closed acidproof resistance to compression reactor with reaction liquid material two, open the circulation pump is added
7.5kg mass concentrations are 25% sodium nitrite solution (containing 2% sodium iodide), are passed through oxygen, and oxygen flow is 0.4m3/ h, rises
Temperature reacts 1.5~2h to 55~90 DEG C, cools down to obtain improved PFS solution 600kg.
Embodiment 3
By 84kg polyaluminiums waste slag of aluminum, (aluminium content is with Al2O39% is calculated as, silicone content is with SiO2Be calculated as 4%), 126kg sulphur
(iron content is with Fe for acid type ferrous acid2O38.4% is calculated as, acidity is calculated as 24.4%) mixing input pretreatment reaction kettle with sulfuric acid, rises
To 45~65 DEG C, stirring reaction 1h, press filtration obtains 140kg reaction liquid materials one to temperature.
By 350kg green vitriols, (iron content is with Fe2O3Be calculated as 28.6%), (iron content is with Fe for 190kg sulfuric acid types ferrous acid2O3Meter
It is 8.4%, acidity is calculated as 24.4%) with sulfuric acid and 160kg water puts into pretreatment reaction kettle, and 0.5h is stirred under normal temperature, obtains 700kg
Reaction liquid material two.
Will be during reaction liquid material one to put into closed acidproof resistance to compression reactor with reaction liquid material two, open the circulation pump is added
10.5kg mass concentrations are 25% sodium nitrite solution (containing 2% sodium iodide), are passed through oxygen, and oxygen flow is 0.56m3/ h,
55~90 DEG C are warming up to, 1.5~2h is reacted, improved PFS solution 840kg is cooled down to obtain.
The energy saving and environment friendly improved PFS effect evaluation method of the present invention：
Sewage source is certain printing and dyeing mill's raw water, and COD of sewage is 306.9mg/L, and modified PFS and PFS is pressed 1 ‰ dosage
Add in sewage, adjust pH to 7,120min is stood after stirring coagulation, observe supernatant colourity, detect supernatant C OD indexs.It is real
Modified PFS is similar with the content parameter of PFS used by testing, and iron content is with Fe2O311.3% is calculated as, basicity is 14%.COD of sewage
And clearance effect is shown in Table 1.
Table 1 is modified PFS and PFS to the contrast of certain disposal effect of dyeing wastewater
| COD(mg/L) | COD clearances (%) | |
| Raw water | 306.9 | - |
| Modified PFS | 106.5 | 65.3 |
| PFS | 183.3 | 40.3 |
Data can be obtained from table, and in the case of dosage identical, the COD removal effects of the PFS that is modified are more excellent.
With above-mentioned according to desirable embodiment of the invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property scope is not limited to the content on specification, it is necessary to its technical scope is determined according to right.
Claims (4)
1. a kind of preparation technology of energy saving and environment friendly improved PFS, it is characterized in that：Comprise the following steps：
(1) by polyaluminium waste slag of aluminum and sulfuric acid type ferrous acid input pretreatment reaction kettle, 45~65 DEG C, stirring reaction are warming up to
0.5~1h, press filtration must react liquid material one；
(2) by green vitriol and sulfuric acid type ferrous acid input pretreatment reaction kettle, 0.5~1h is stirred under normal temperature, liquid material two must be reacted；
(3) will be during reaction liquid material one and reaction liquid material two put into closed acidproof resistance to compression reactor, open the circulation pump adds catalyst
Solution and co-catalyst solution, are passed through oxygen, are warming up to 55~90 DEG C, react 1.5~2h, cool down improved PFS is molten
Liquid；
Polyaluminium waste slag of aluminum is to produce aluminium polychloride finished product bottom residues through the semi-solid material after press filtration in step (1),
Polyaluminium waste slag of aluminum contains aluminium polychloride and a small amount of silicon, and its aluminium content is with Al2O37~12% are calculated as, silicone content is with SiO2Meter
It is 3~7%；
Polyaluminium waste slag of aluminum and the mass ratio of sulfuric acid type ferrous acid are 1 in step (1)：1.5；
Sulfuric acid type ferrous acid in step (1) and step (2), its iron content is with Fe2O31~18% is calculated as, acidity is calculated as with sulfuric acid
4~25%；
The iron content of green vitriol is with Fe in step (2)2O3It is calculated as 18~30%；
The iron content of reaction liquid material two is with Fe in step (2)2O312~18% are calculated as, basicity is 50~70%；
The mass ratio that adds of reaction liquid material one and reaction liquid material two is 1 in step (3)：5.
2. the preparation technology of a kind of energy saving and environment friendly improved PFS according to claim 1, it is characterized in that：It is described
The step of (3) in catalyst be natrium nitrosum, co-catalyst is sodium iodide.
3. the preparation technology of a kind of energy saving and environment friendly improved PFS according to claim 2, it is characterized in that：It is described
The step of (3) in catalyst and co-catalyst natrium nitrosum and sodium iodide be made into mass concentration when in use distinguish 25% He
2% mixed aqueous solution, dosage is react the mass of liquid material two 1.5~2%.
4. the preparation technology of a kind of energy saving and environment friendly improved PFS according to claim 1, it is characterized in that：It is described
The step of (3) in oxygen intake be excessive.
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| CN106241843A (en) * | 2016-07-19 | 2016-12-21 | 武汉理工大学 | A kind of method that aluminium hydroxide is prepared in polyaluminium waste slag of aluminum acid system recovery |
| CN109081382A (en) * | 2018-10-25 | 2018-12-25 | 马鞍山健鼎化工有限公司 | A kind of processing technology of bodied ferric sulfate |
| CN111453826B (en) * | 2020-04-03 | 2022-02-08 | 中国科学院合肥物质科学研究院 | Micro-nano porous polyaluminium coagulant aid and preparation method and application thereof |
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|---|---|---|---|---|
| CN1052295A (en) * | 1989-12-08 | 1991-06-19 | 樊冠球 | Basic ferric sulfate coagulant for water treatment |
| CN1421393A (en) * | 2002-12-19 | 2003-06-04 | 鲍文林 | Prepn process of liquid polymerized ferric sulfate by means of oxidizing catalyst |
| CN101249987A (en) * | 2008-03-17 | 2008-08-27 | 李绍通 | Method for synthesizing polymeric ferric sulphate |
| CN103864154A (en) * | 2014-03-27 | 2014-06-18 | 李科 | Production method of liquid polymeric ferric sulfate water purifying agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100492035B1 (en) * | 2002-10-28 | 2005-05-30 | 박경호 | manufacturing method of ploy ferric sulfate |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1052295A (en) * | 1989-12-08 | 1991-06-19 | 樊冠球 | Basic ferric sulfate coagulant for water treatment |
| CN1421393A (en) * | 2002-12-19 | 2003-06-04 | 鲍文林 | Prepn process of liquid polymerized ferric sulfate by means of oxidizing catalyst |
| CN101249987A (en) * | 2008-03-17 | 2008-08-27 | 李绍通 | Method for synthesizing polymeric ferric sulphate |
| CN103864154A (en) * | 2014-03-27 | 2014-06-18 | 李科 | Production method of liquid polymeric ferric sulfate water purifying agent |
Non-Patent Citations (1)
| Title |
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| "利用工业废弃物制备聚合硫酸铁铝硅混凝剂";张开仕等;《化工学报》;20080930;第59卷(第9期);第2361-2365页 * |
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