CN108557970A - A kind of poly-ferric sulfate chloride aluminium flocculating agent and preparation method thereof - Google Patents
A kind of poly-ferric sulfate chloride aluminium flocculating agent and preparation method thereof Download PDFInfo
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- CN108557970A CN108557970A CN201810472862.2A CN201810472862A CN108557970A CN 108557970 A CN108557970 A CN 108557970A CN 201810472862 A CN201810472862 A CN 201810472862A CN 108557970 A CN108557970 A CN 108557970A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/14—Sulfates
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Abstract
The invention discloses a kind of poly-ferric sulfate chloride aluminium flocculating agent and preparation method thereof, the preparation method of the poly-ferric sulfate chloride aluminium flocculating agent includes：Hydrochloric acid is added in titanium dioxide industry by-product and is heated to 40~50 DEG C and is modified reaction；Then red mud is carried into scum and modified titanium dioxide industry by-product is placed in ultrasound reactor and is mixed and heated to 100~110 DEG C, mixed liquor is obtained by the reaction；The mixed liquor is subjected to cold filtration again, oxidant is added into obtained filtrate and carries out polymerisation.The present invention carries scum and titanium dioxide industry by-product as the primary raw material for preparing poly-ferric sulfate chloride aluminium flocculating agent using red mud, by introducing a small amount of ferrous ion in the system of ferric ion, it is not required to restore the poly-ferric sulfate chloride aluminium flocculating agent that one step of original ferric ion is prepared, flocculating effect is good, high to the removal rate of TP, COD and coloration.
Description
Technical field
The present invention relates to water-treatment technology field, in particular to a kind of poly-ferric sulfate chloride aluminium flocculating agent and its
Preparation method.
Background technology
Currently, common water treatment inorganic coagulant includes mainly two major classes agent, that is, molysite and aluminium salt in the market.Molysite has
There are the advantages such as hydrolysis is fast, alumen ustum volume is big, closely knit, fast, the intensity height of sedimentation, however remaining coloration is big to be lacked there is also being discharged
It falls into.And the advantage that aluminium salt has the remaining coloration of water outlet small, but there at the same time have that hydrolysis is slow, alumen ustum is small, sedimentation is slow etc. to be scarce
It falls into.
Poly-ferric sulfate chloride aluminium grows up on the basis of bodied ferric sulfate, has both the excellent water purification of aluminium salt
Effect and the fast advantage of molysite sinking speed, and it is widely used in industrial wastewater, sanitary sewage disposal and sludge dewatering.
However, at present in the production of poly-ferric sulfate chloride aluminium flocculating agent, main preparation process has direct oxidation method and urges
Change oxidizing process.Catalytic oxidation has the advantages such as at low cost, the reaction time is shorter and is applied in the industrial production extensively.However
The source of aluminium is essentially all the compound containing aluminium using industrial agent.In addition, common catalyst is also to adopt in catalytic oxidation
With industrial agent such as sodium nitrite, nitric acid etc..This has increased considerably the production cost of poly-ferric sulfate chloride aluminium flocculating agent, unfavorable
With carrying out large-scale industrial production.Therefore, how further poly-ferric sulfate chloride aluminum flocculation is prepared using the by-product of aluminium
Agent water purification agent turns waste into wealth to realize, and optimizes reaction process, improves reaction efficiency, reduces reaction process, becomes and grind now
The hot spot studied carefully.
By the end of 2017, China's titanium dioxide yield had reached 286.95 ten thousand tons, is sure to occupy first place in the world, became titanium dioxide life
Production and consumption big country.Although China's titanium dioxide industry achieves immense success, for many years by titanium resource, production technology and dress
The condition of the factors such as standby, material limits, and mostly uses Production By Sulfuric Acid Process.According to statistics, in sulfate process titanium dioxide production process, 1 is often produced
Ton titanium dioxide will generate 8~10 tons of by-product sulfuric acid.And the sulfuric acid containing 15~25% sulfuric acid and 10~15% in by-product sulfuric acid
Ferrous iron, while also containing Al2(SO4)3、MgSO4Equal inorganic salts and metatitanic acid, complex treatment process, difficulty are big.
Titanium dioxide accounts for about world's white face as a kind of current application amount maximum also most wide inorganic white pigment, yield
Expect the 80% of total output.And sulfuric acid process is to produce the main method of titanium dioxide at present, this method produces 1 ton of titanium dioxide, and generation is secondary
8~10 tons of product.And the ferrous sulfate containing 15~25% sulfuric acid and 10~15% in by-product sulfuric acid, while also containing Al2
(SO4)3And the inorganic salts such as MgSO4 and metatitanic acid, complex treatment process, difficulty it is big.And containing there are many miscellaneous in the by-product sulfuric acid
Matter is unable to direct reuse and arbitrarily discharge, and therefore, the comprehensive utilization and environmental pollution of titanium dioxide industry by-product sulfuric acid are also current
The problem of technical field urgent need to resolve.
And the red mud that the red mud that aluminium industry generates generates after carrying iron carries scum without industrial value, takes mostly at present
The method of dry heap or wet heap is stored up, and the dust that the red mud dried proposes scum formation is flown upward everywhere, destroys ecological environment, and
Polluted underground water.
So far, it has not seen and carries scum using red mud and titanium dioxide industry by-product prepares poly-ferric sulfate chloride aluminium
Report.
Invention content
In view of this, a kind of poly-ferric sulfate chloride aluminium flocculating agent provided by the invention and preparation method thereof, better gram
The above-mentioned problems of the prior art and defect are taken, the present invention carries scum and titanium dioxide industry by-product as system using red mud
The primary raw material of standby poly-ferric sulfate chloride aluminium flocculating agent, it is excellent that obtained poly-ferric sulfate chloride aluminium flocculating agent has both aluminium salt
Purifying water effect and the fast advantage of molysite sinking speed, flocculating effect is good, and the settling of floccus time is short, is gone to TP, COD and coloration
Except rate height, while also overcoming and the murder by poisoning of human body and molysite are easy in aluminium residual water body to make the deficiency of water body flavescence, blackening, and
It is widely used in industrial wastewater, sanitary sewage disposal and sludge dewatering.
A kind of preparation method of poly-ferric sulfate chloride aluminium flocculating agent, includes the following steps：
(1) hydrochloric acid is added to the titanium dioxide industry pair of sulfur acid 22.8~28.17% and ferrous sulfate 6.65~8.82%
It in product and is heated to 40~50 DEG C and is modified reaction, obtain modified titanium dioxide industry by-product；
(2) red mud of salic 6.35~8.66% and iron oxide 55.1~68.3% is carried into scum and modified titanium white
Powder industrial by-products are mixed and heated to 100~110 DEG C, and mixed liquor is obtained by the reaction；
(3) mixed liquor is subjected to cold filtration, oxidant is added into obtained filtrate and carries out polymerisation.
Further, in step (1), the hydrochloric acid is the technical hydrochloric acid of 8~10mol/L, the hydrochloric acid and the titanium white
The mass ratio of powder industrial by-products is 1：8~10.
Further, in step (1), the modified-reaction time is 30~40min.
Further, in step (2), it is 12 that the red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,
~16：82~90.
Further, in step (2), the red mud is carried into scum, ultrasonic wave is added with modified titanium dioxide industry by-product
Hybrid Heating is carried out in reactor.
Further, in step (2), the reaction time is 60~100min.
Further, in step (3), the mixture is cooled to 80~85 DEG C of filterings.
Further, in step (3), the oxidant is potassium chlorate, sodium chlorate or hydrogen peroxide.
Further, in step (3), the mass ratio of the oxidant and filtrate is 0.8~1.0：100.
The present invention also provides a kind of poly-ferric sulfate chloride aluminium flocculating agent, the poly-ferric sulfate chloride aluminium flocculating agent by
The preparation method of above-mentioned poly-ferric sulfate chloride aluminium flocculating agent.
Compared with prior art, the beneficial effect of a kind of poly-ferric sulfate chloride aluminium flocculating agent of the invention and preparation method thereof
Fruit is：
(1) present invention carries scum and titanium dioxide industry by-product as preparing poly-ferric sulfate chloride aluminum flocculation using red mud
On the one hand the primary raw material of agent is modified titanium dioxide industry by-product by using hydrochloric acid, be coordinated using the height of chlorion
Effect makes the transition metal in titanium white by product acid be coordinated therewith, and the kinetics for reducing follow-up mixed acid and metal oxide hinders
Power improves penetration capacity and the rapid reaction of follow-up mixed acid and metal oxide is promoted to complete, on the other hand by trivalent
A small amount of ferrous ion is introduced in the system of iron ion, is not required to restore one step of original ferric ion polyaluminium sulphur is prepared
Sour iron aluminium flocculating agent, the flocculant have both the excellent purifying water effect of aluminium salt and the fast advantage of molysite sinking speed, flocculating effect
Good, the settling of floccus time is short, high to the removal rate of TP, COD and coloration, while also overcoming the poison in aluminium residual water body to human body
Evil and molysite are easy to make the deficiency of water body flavescence, blackening, and it is de- to be widely used in industrial wastewater, sanitary sewage disposal and sludge
Water.
(2) preparation method of poly-ferric sulfate chloride aluminium flocculating agent of the invention is simple for process, and raw material is easy to get, and low energy consumption,
It is easy to operate；Production cost is not only considerably reduced, but also realizes red mud and carries the comprehensive of scum and titanium dioxide industry by-product
It closes and utilizes, save red mud and carry the commission handling of scum and efficiently solve titanium dioxide industry by-product sulfuric acid and be unable to direct reuse
And the problem that neutralisation treatment is of high cost, reduce environmental pollution.
(3) further, ultrasonic wave is added with modified titanium dioxide industry by-product by the way that red mud is carried scum in the present invention
Hybrid Heating reaction is carried out in reactor, is acted on using ultrasonic wave " cavitation ", improves metal oxide and neutralization reaction occurs with acid
Efficiency, red mud is put forward into active ingredient most in scum and is transferred in liquid phase, red mud is greatly improved and carries the molten of scum
Extracting rate.
To enable the above objects, features and advantages of the present invention to be clearer and more comprehensible, preferred embodiment cited below particularly is made detailed
It is described as follows.
Specific implementation mode
To facilitate the understanding of the present invention, it elaborates to technical scheme of the present invention with reference to the mode of embodiment,
Many details are elaborated in the following description in order to fully understand the present invention.
But the invention can be embodied in many other ways as described herein, those skilled in the art can be with
Similar improvement is done without violating the connotation of the present invention, therefore the present invention is not limited to the specific embodiments disclosed below.
Unless otherwise defined, all technologies used herein and scientific terminology have and the common skill of fields of the present invention
The normally understood identical meaning of art personnel.When there is a conflict, the definition in this specification shall prevail.
Term as used herein：
Term "comprising" used herein, " comprising ", " having ", " containing " or its any other deformation, it is intended that covering
Non-exclusionism includes.For example, composition, step, method, product or device comprising listed elements are not necessarily limited to those and want
Element, but may include not expressly listed other elements or such composition, step, method, product or device it is intrinsic
Element.
Conjunction " by ... form " exclude any element that do not point out, step or component.If in claim,
This phrase will make claim be closed, so that it is not included the material in addition to the material of those descriptions, but relative
Except customary impurities.When phrase " by ... form " be rather than immediately following theme in the clause that appears in claim main body after
When, only it is limited to the element described in the clause；Other elements be not excluded the claim as a whole it
Outside.
Equivalent, concentration or other values or parameter are excellent with range, preferred scope or a series of upper limit preferred values and lower limit
When the Range Representation that choosing value limits, this, which should be understood as, specifically discloses by any range limit or preferred value and any range
Any pairing of lower limit or preferred value is formed by all ranges, regardless of whether the range separately discloses.For example, when open
When range " 1~5 ", described range should be interpreted as including range " 1~4 ", " 1~3 ", " 1~2 ", " 1~2 and 4~
5 ", " 1~3 and 5 " etc..When numberical range is described herein, unless otherwise stated, otherwise range intention includes its end
Value and all integers and score in the range.
"and/or" is used to indicate that one of illustrated situation or both may to occur, for example, A and/or B includes (A
And B) and (A or B).
A kind of preparation method of poly-ferric sulfate chloride aluminium flocculating agent, includes the following steps：
(1) hydrochloric acid is added to the titanium dioxide industry pair of sulfur acid 22.8~28.17% and ferrous sulfate 6.65~8.82%
It in product and is heated to 40~50 DEG C and is modified reaction, obtain modified titanium dioxide industry by-product.
(2) red mud of salic 6.35~8.66% and iron oxide 55.1~68.3% is carried into scum and modified titanium white
Powder industrial by-products are mixed and heated to 100~110 DEG C, and mixed liquor is obtained by the reaction.
(3) mixed liquor is subjected to cold filtration, oxidant is added into obtained filtrate and carries out polymerisation.
In above-mentioned titanium dioxide industry by-product：It is 22.8% that the content of sulfuric acid is specific enumerable, 23.5%, 25.35%,
26.68% or 28.17% etc.；The concrete content of ferrous sulfate can be enumerated as 6.65%, 7.03%, 7.52%, 7.86%,
8.25% or 8.82% etc..
Above-mentioned red mud carries in scum：The specific enumerable content of aluminium oxide is 6.35%, 6.86%, 7.31%, 7.85%
Or 8.66% etc.；The specific enumerable content of iron oxide is 55.1%, 58.5%, 60.3%, 62.8%, 65.6% or 68.3%
Deng.
Preferably, in step (1), the hydrochloric acid is 8~10mol/L such as 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/
The mass ratio of the technical hydrochloric acid of L or 10mol/L, the hydrochloric acid and the titanium dioxide industry by-product is 1：8~10 such as 1：8、1：
8.5、1：9、1：9.5 or 1：10 etc..
Preferably, in step (1), the modified-reaction time is 30~40min such as 30min, 32min, 35min, 38min
Or 40min etc..
It should be noted that in step (1), titanium dioxide industry by-product is modified by using hydrochloric acid, utilizes chlorine
The high coordination effect of ion makes the transition metal in titanium white by product acid be coordinated therewith, reduces follow-up mixed acid and metal oxide
Kinetics resistance improves penetration capacity and the rapid reaction of follow-up mixed acid and metal oxide is promoted to complete.
Preferably, in step (2), mass ratio that the red mud carries scum and modified titanium dioxide industry by-product is 12~
16：82~90.
Above-mentioned red mud carry scum and modified titanium dioxide industry by-product mass ratio it is specific enumerable be 12：82、13：
85、14：88、16：82、16：85 or 16：90 etc..
Preferably, in step (2), the red mud is carried into scum and modified titanium dioxide industry by-product addition ultrasonic wave is anti-
It answers and carries out Hybrid Heating in device.
It should be noted that in step (2), added with modified titanium dioxide industry by-product by the way that the red mud is carried scum
Enter progress Hybrid Heating reaction in ultrasound reactor, acted on using ultrasonic wave " cavitation ", improves metal oxide and occur with acid
Red mud is put forward active ingredient most in scum and is transferred in liquid phase by the efficiency of neutralization reaction.
Preferably, in step (2), the reaction time be 60~100min such as 60min, 70min, 80min, 90min or
100min。
Preferably, in step (3), the mixture is cooled to 80~85 DEG C of filterings.
Preferably, in step (3), the oxidant is potassium chlorate, sodium chlorate or hydrogen peroxide.
Preferably, in step (3), the mass ratio of the oxidant and filtrate is 0.8~1.0：100.
Above-mentioned oxidant and the mass ratio of filtrate it is specific enumerable be 0.8：100、0.85：100、0.9：100、0.95：100
Or 1.0：100 etc..
The present invention also provides a kind of poly-ferric sulfate chloride aluminium flocculating agent, the poly-ferric sulfate chloride aluminium flocculating agent by
The preparation method of above-mentioned poly-ferric sulfate chloride aluminium flocculating agent.
The present invention carries scum and titanium dioxide industry by-product as preparing poly-ferric sulfate chloride aluminium flocculating agent using red mud
Primary raw material, obtained poly-ferric sulfate chloride aluminium flocculating agent has both the excellent purifying water effect of aluminium salt and molysite sinking speed
Fast advantage, flocculating effect is good, and flco is big and closely knit, and the settling of floccus time is short, has good coagulation effect, to TP, COD and
The removal rate of coloration is high, while also overcoming and being easy to make water body flavescence, blackening to the murder by poisoning of human body and molysite in aluminium residual water body
Deficiency, and be widely used in industrial wastewater, sanitary sewage disposal and sludge dewatering；The present invention not only considerably reduces life
Cost is produced, and realizes the comprehensive utilization that red mud carries scum and titanium dioxide industry by-product, saves the committee that red mud carries scum
It holds in the palm handling and solves the problems, such as that titanium dioxide industry by-product ferrous sulfate is unable to direct reuse and stores up everywhere, reduce
Environmental pollution；The preparation method of the poly-ferric sulfate chloride aluminium flocculating agent of the present invention is simple for process, and raw material is easy to get.
In addition, it is necessary to explanation, red mud carry the iron ion in scum all be ferric ion, with sulfuric acid reaction after produce
Be ferric sulfate and iron chloride.By taking ferric sulfate as an example, the molar ratio of iron ion and sulfate radical is 1：1.5.And polyaluminium sulfuric acid
Iron aluminium is by hydroxyl (OH-) becoming inorganic polymer from low-molecular inorganic after connection, the condition for introducing hydroxyl must be sulfuric acid
The negative electrical charge of radical ion is inadequate, needs hydroxyl to supplement, it is clear that the charge of ferric sulfate and iron chloride just balances.So introducing two
After valence iron ion, when divalent is oxidized to trivalent, ferric ion in system will prehydrolysis, generate during a large amount of hydroxyl comes
And charge.Polymerisation will occur for these hydroxyls, produce poly-ferric sulfate chloride aluminium.It is usually first by portion in the prior art
Divide ferric ion reduction, to obtain ferrous ion；And the present invention carries scum and titanium dioxide industry by-product system using red mud
Standby poly-ferric sulfate chloride aluminium can be prepared directly with ferric ion, energy consumption it is not necessary that ferric ion is restored ferrous ion
It is low, it is easy to operate.
To facilitate the understanding of the present invention, the technical solution further illustrated the present invention with reference to embodiment.Applicant
Statement, the present invention are illustrated by the following examples detailed process equipment and the technological process of the present invention, but the present invention not office
It is limited to following detailed process equipments and technological process, that is, does not mean that the present invention should rely on above-mentioned detailed process equipment and technique stream
Cheng Caineng is implemented.Person of ordinary skill in the field is it will be clearly understood that any improvement in the present invention, to each original of product of the present invention
The equivalence replacement of material and the addition of auxiliary element, the selection of concrete mode etc. all fall within protection scope of the present invention and open model
Within enclosing.
Embodiment 1
(1) technical hydrochloric acid of 8mol/L is added to the titanium dioxide industry pair of sulfur acid 22.8% and ferrous sulfate 8.82%
In product, and 40 DEG C of reaction 40min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid and the titanium
The mass ratio of white powder industrial by-products is 1：8.
(2) red mud of salic 6.35% and iron oxide 68.3% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 100 DEG C, reacts 100min, obtains mixed liquor；Wherein
It is 12 that red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：82.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 15min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 0.8：100.
Embodiment 2
(1) technical hydrochloric acid of 8.5mol/L is added to the titanium dioxide industry of sulfur acid 23.5% and ferrous sulfate 8.25%
In by-product, and 45 DEG C of reaction 40min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid with it is described
The mass ratio of titanium dioxide industry by-product is 1：8.5.
(2) red mud of salic 6.86% and iron oxide 65.6% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 105 DEG C, reacts 90min, obtains mixed liquor；It is wherein red
It is 13 that mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：85.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 20min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 0.85：100.
Embodiment 3
(1) technical hydrochloric acid of 9mol/L is added to the titanium dioxide industry of sulfur acid 25.35% and ferrous sulfate 7.86%
In by-product, and 50 DEG C of reaction 35min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid with it is described
The mass ratio of titanium dioxide industry by-product is 1：9.
(2) red mud of salic 7.31% and iron oxide 60.3% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 105 DEG C, reacts 80min, obtains mixed liquor；It is wherein red
It is 14 that mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：88.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 25min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 0.9：100.
Embodiment 4
(1) technical hydrochloric acid of 9.5mol/L is added to the titanium dioxide work of sulfur acid 26.68% and ferrous sulfate 7.52%
In industry by-product, and 50 DEG C of reaction 30min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid and institute
The mass ratio for stating titanium dioxide industry by-product is 1：9.5.
(2) red mud of salic 7.85% and iron oxide 58.5% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 105 DEG C, reacts 70min, obtains mixed liquor；It is wherein red
It is 16 that mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：82.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 30min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 0.95：100.
Embodiment 5
(1) technical hydrochloric acid of 10mol/L is added to the titanium dioxide industry of sulfur acid 28.17% and ferrous sulfate 6.65%
In by-product, and 50 DEG C of reaction 30min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid with it is described
The mass ratio of titanium dioxide industry by-product is 1：10.
(2) red mud of salic 8.66% and iron oxide 55.1% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 100 DEG C, reacts 100min, obtains mixed liquor；Wherein
It is 16 that red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：85.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 15min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 1.0：100.
Embodiment 6
(1) technical hydrochloric acid of 8mol/L is added to the titanium dioxide industry of sulfur acid 25.35% and ferrous sulfate 7.86%
In by-product, and 50 DEG C of reaction 30min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid with it is described
The mass ratio of titanium dioxide industry by-product is 1：9.
(2) red mud of salic 7.31% and iron oxide 60.3% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 100 DEG C, reacts 100min, obtains mixed liquor；Wherein
It is 14 that red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：88.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 15min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 1.0：100.
Embodiment 7
(1) technical hydrochloric acid of 9mol/L is added to the titanium dioxide industry of sulfur acid 25.35% and ferrous sulfate 6.65%
In by-product, and 50 DEG C of reaction 30min are heated to, obtain modified titanium dioxide industry by-product；Wherein technical hydrochloric acid with it is described
The mass ratio of titanium dioxide industry by-product is 1：10.
(2) red mud of salic 6.35% and iron oxide 62.8% is carried to the titanium of the modification of scum and step (1) preparation
White powder industrial by-products, which are added in ultrasound reactor, is mixed and heated to 100 DEG C, reacts 100min, obtains mixed liquor；Wherein
It is 16 that red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：90.
(3) mixed liquor prepared by step (2) is cooled to 80~85 DEG C of filterings, oxidation is then added into obtained filtrate
Agent potassium chlorate, while stirring and so that oxidation and polymerisation are carried out, it is stirred to react 30min, obtains poly-ferric sulfate chloride
Aluminium flocculating agent；Wherein oxidant potassium chlorate and the mass ratio of filtrate are 0.9：100.
To Examples 1 to 7 prepare indices include：Appearance, Quan Tie, aluminium oxide and basicity content examined
It surveys, testing result is as shown in table 1.
Table 1
The polyaluminum sulfate that poly-ferric sulfate chloride aluminium flocculating agent prepared by the embodiment of the present invention 1~7 is sold with market
Iron and flocculant of polymeric aluminium chloride compare the removal effect of TP and COD in water sample, as shown in table 2 below.Wherein, water sample is derived from
Fourth mountains and rivers river water, the content of TP is 8.36mg/L before handling, and the content of COD is 79.8mg/L, and coloration is 84 times.
Table 2
Can be obtained by upper table 1, the embodiment of the present invention 1~7 prepare poly-ferric sulfate chloride aluminium in water sample TP and
The removal effect of COD obviously than commercially available polymeric ferric sulfate flocculant and commercially available flocculant of polymeric aluminium chloride in water sample TP and
The removal effect of COD is more preferable；In addition, the embodiment of the present invention 1~7 prepare poly-ferric sulfate chloride aluminium to the coloration in water sample
Removal effect it is obviously more preferable to the removal effect of the coloration in water sample than commercially available polymeric ferric sulfate flocculant, polymerize chlorine with commercially available
It is suitable to the removal effect of the coloration in water sample to change aluminium flocculating agent.
The preferred embodiment of the present invention is above are only, is not intended to restrict the invention, for those skilled in the art
For member, inventive formulation and preparation process can have various modifications and variations.All within the spirits and principles of the present invention, institute
Any modification, equivalent substitution, improvement and etc. of work, should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of poly-ferric sulfate chloride aluminium flocculating agent, it is characterised in that：Include the following steps：
(1) hydrochloric acid is added to the titanium dioxide industry by-product of sulfur acid 22.8~28.17% and ferrous sulfate 6.65~8.82%
In and be heated to 40~50 DEG C and be modified reaction, obtain modified titanium dioxide industry by-product；
(2) red mud of salic 6.35~8.66% and iron oxide 55.1~68.3% is carried into scum and modified titanium dioxide work
Industry by-product is mixed and heated to 100~110 DEG C, and mixed liquor is obtained by the reaction；
(3) mixed liquor is subjected to cold filtration, oxidant is added into obtained filtrate and carries out polymerisation.
2. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (1)
In, the hydrochloric acid is the technical hydrochloric acid of 8~10mol/L, and the mass ratio of the hydrochloric acid and the titanium dioxide industry by-product is 1：8
~10.
3. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (1)
In, the modified-reaction time is 30~40min.
4. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (2)
In, it is 12~16 that the red mud, which carries scum and the mass ratio of modified titanium dioxide industry by-product,：82~90.
5. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (2)
In, the red mud is carried into scum and carries out Hybrid Heating with modified titanium dioxide industry by-product addition ultrasound reactor.
6. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (2)
In, the reaction time is 60~100min.
7. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (3)
In, the mixture is cooled to 80~85 DEG C of filterings.
8. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (3)
In, the oxidant is potassium chlorate, sodium chlorate or hydrogen peroxide.
9. the preparation method of poly-ferric sulfate chloride aluminium flocculating agent according to claim 1, it is characterised in that：Step (3)
In, the mass ratio of the oxidant and filtrate is 0.8~1.0：100.
10. a kind of poly-ferric sulfate chloride aluminium flocculating agent, it is characterised in that：The poly-ferric sulfate chloride aluminium flocculating agent is by right
It is required that the preparation method of 1~9 any one of them poly-ferric sulfate chloride aluminium flocculating agent.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100576731B1 (en) * | 2003-12-04 | 2006-05-10 | 케이씨 주식회사 | Method for preparing porous and alkaline hematite material and water treatment using the material |
| CN101423259A (en) * | 2008-11-18 | 2009-05-06 | 华南师范大学 | Preparation method of solid polymeric aluminum ferric sulfate |
| CN101786702A (en) * | 2009-01-22 | 2010-07-28 | 湖南化工研究院 | Special water treatment agent FPAS-4 for treating papermaking wastewater and preparation method thereof |
| 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 |
| CN103086489A (en) * | 2013-02-07 | 2013-05-08 | 天津水泥工业设计研究院有限公司 | Method for preparing flocculant polyaluminum ferric chloride from red mud |
| CN103771572A (en) * | 2014-02-12 | 2014-05-07 | 重庆大学 | Preparation method of polymerization chlorination zinc iron sulfate flocculating agent |
| CN104085969A (en) * | 2014-07-17 | 2014-10-08 | 广西平果锋华科技有限公司 | Method for preparing compound type multi-element flocculating agent aluminum ferric sulfate chloride polysilicate by utilizing waste acid |
-
2018
- 2018-05-17 CN CN201810472862.2A patent/CN108557970B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100576731B1 (en) * | 2003-12-04 | 2006-05-10 | 케이씨 주식회사 | Method for preparing porous and alkaline hematite material and water treatment using the material |
| CN101423259A (en) * | 2008-11-18 | 2009-05-06 | 华南师范大学 | Preparation method of solid polymeric aluminum ferric sulfate |
| CN101786702A (en) * | 2009-01-22 | 2010-07-28 | 湖南化工研究院 | Special water treatment agent FPAS-4 for treating papermaking wastewater and preparation method thereof |
| 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 |
| CN103086489A (en) * | 2013-02-07 | 2013-05-08 | 天津水泥工业设计研究院有限公司 | Method for preparing flocculant polyaluminum ferric chloride from red mud |
| CN103771572A (en) * | 2014-02-12 | 2014-05-07 | 重庆大学 | Preparation method of polymerization chlorination zinc iron sulfate flocculating agent |
| CN104085969A (en) * | 2014-07-17 | 2014-10-08 | 广西平果锋华科技有限公司 | Method for preparing compound type multi-element flocculating agent aluminum ferric sulfate chloride polysilicate by utilizing waste acid |
Non-Patent Citations (1)
| Title |
|---|
| 陈佛顺主编: "《有色冶金环境保护》", 30 November 1984, 冶金工业出版社 * |
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