CN104692467B - Preparation method of polyferric sulfate - Google Patents
Preparation method of polyferric sulfate Download PDFInfo
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- CN104692467B CN104692467B CN201510080038.9A CN201510080038A CN104692467B CN 104692467 B CN104692467 B CN 104692467B CN 201510080038 A CN201510080038 A CN 201510080038A CN 104692467 B CN104692467 B CN 104692467B
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Abstract
The invention provides a preparation method of polyferric sulfate. The method is that a sulfuric acid aqueous solution and ferrous sulfate are mixed to obtain a mixing solution of which the pH is 0.5 to 1.5; the mixing solution and hydrogen peroxide respectively individually flow through independent flowing channels and then are synchronously poured into a reaction system to react to obtain polyferric sulfate. With the adoption of the method, the oxidizing capacity of hydrogen peroxide can be improved, the rate of converting ferrous ions into ferric ions can be increased, and moreover, ferrous ions and hydrogen peroxide can fully contact and rapidly react; therefore, the problem of decomposing of hydrogen peroxide at a high temperature or strong acid condition in the prior art can be effectively solved, the dosage of hydrogen peroxide can be reduced, the cost input can be decreased, the operation process is simplified, and the reaction time is greatly reduced. The quality of polyferric sulfate prepared by the method meets indicators as specified by national standard on top quality goods; with the adoption of the polyferric sulfate to treat wastewater, the COD of drained water can be stabilized to be less than or equal to 86mg/L, so that the method is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of bodied ferric sulfate, belong to Water body cleansing agent technical field.
Technical background
Bodied ferric sulfate is a kind of new and effective inorganic polymer flocculant that the eighties in 20th century grows up, its liquid
Body is the sticky shape of rufous, and solid is then faint yellow unformed powder, is highly soluble in water, can be configured to the solution of any concentration.
With traditional flocculant compared with ferric trichloride, aluminum sulfate, chloro sulphuric acid iron, aluminium chloride etc., bodied ferric sulfate has life
Produce low cost, purification process is adding less, ph value scope that is adapting to water body is wide, impurity (cod, heavy metal, suspension etc.) removes
Rate is high, debris concentration is low, alumina blossom particles are big, sinking speed is fast, good decolorizing effect the advantages of, be widely used in life and drink
The purified treatment of the water bodys such as water, water for industrial use, municipal sewage and industrial wastewater.
Preparation technology currently for bodied ferric sulfate mainly has direct oxidation method and catalytic oxidation.Great majority polymerization
The preparation of ferric sulfate adopts direct oxidation method, adds oxidant (h in process of production2o2、kclo3、hno3Deng) aoxidized
Process, this method process route is relatively simple, can reduce equipment investment and production link for industrial production, thus reducing production
Cost.Wherein, the simple production process of potassium chlorate oxidizing process, reaction efficiency height, no air pollution, product stability are good, and produce
Coagulant and bactericide can be doubled as containing chlorate in product, but in product because remain the chlorion of high level and chlorate anions from
Son and be unsuitable for drinking water treatment, and potassium chlorate is expensive, causes product cost high, is unfavorable for industrialized production；Nitric acid
The cost of oxidizing process is relatively low, and product design is high, easily makes solid-state product, but the no generating in reaction2Pollute the environment, need to increase
Device for absorbing tail gas；And hydrogen peroxide oxidation process produces the technique of bodied ferric sulfate, because hydrogen peroxide is under sour environment
A kind of strong oxidizer, its reduzate only has water, has not both had pollutant and the generation not having solid waste, and equipment is simple, raw
Product cycle is short, product stability are good, thus hydrogen peroxide has obtained increasing green grass or young crops as a kind of oxidant of environmental protection
Look at, also extremely praised highly using the technique that hydrogen peroxide method produces bodied ferric sulfate.
The technique collection that hydrogen peroxide method produces bodied ferric sulfate aoxidizes, hydrolyzes, polymerization three reacts in a system, its
In, oxidation reaction is that the rate determining step of this series reaction is rapid, and its reaction equation is as follows:
2fcso4+h2o2+h2so4=fe2(so4)3+2h2o
In above-mentioned oxidation reaction process, the factor of the speed and yield that affect this reaction is many, including peroxide
Change the consumption of hydrogen, the consumption of sulfuric acid, reaction temperature, ph value, charging sequence etc., to the analysis of above-mentioned influence factor in Liu Zhirong etc.
Quilt in " bodied ferric sulfate synthesis and performance test " (" Progress ＆ New Products ", the 35-37 page of the 8th phase of volume 17 in 2003) literary composition of people
Detailed record, after they are by investigating to factors such as dioxygen water consumption, oxidizing temperature, the consumption of the concentrated sulfuric acid and feed postition
Find, the feed postition of the concentrated sulfuric acid is the weight factor in impact reaction time, using reaction mid-term dropping sulphate method, and control
A certain amount of flow velocity makes reaction carry out under ph value (ph ＞ 2) as high as possible, so that fe2+It is oxidized to fe3+Speed significantly
Accelerate, the reaction time accordingly shortens hence it is evident that improving efficiency；And determine the optimised process producing bodied ferric sulfate on this basis
Flow process: i.e. at normal temperatures and pressures, in the container of ferrous sulfate heptahydrate and water, under being stirred continuously, first double with certain flow rate dropping
Oxygen water to solution is in rufous, more simultaneously with the quantitative hydrogen peroxide of different in flow rate dropping and the concentrated sulfuric acid until reaction finishes.
Although the bodied ferric sulfate that above-mentioned synthesis technique is obtained is preferable to the flocculating effect of aqueous suspension ofkaolin, its fe3+
Content but fail to reach primes and require, this is because, above-mentioned technique is that hydrogen peroxide first instills the aqueous solution of ferrous sulfate
In, and the ph value of this aqueous solution is 3.7 about, under this ph value environment, the oxidability of hydrogen peroxide is weaker, and is unfavorable for oxygen
Change carrying out rapidly of reaction, so that the hydrogen peroxide not participating in reaction in time is decomposed；Again because this technique is also anti-
Mid-term is answered to add the concentrated sulfuric acid, can be highly exothermic when it is mixed with water, not only further promote the decomposition of hydrogen peroxide, also may be used
Security incident can be caused.As can be seen here, above-mentioned existing process condition cannot avoid the decomposition of hydrogen peroxide so that hydrogen peroxide
Oxidation efficiency reduces, thus increasing the dosage of hydrogen peroxide, not only causing the increase of production cost, also diluting reaction
Liquid, leads to the fe in product3+Content fails to reach the requirement of primes.If solved the above problems, then be accomplished by anti-
Improve the oxidability of hydrogen peroxide during answering as far as possible, be to strengthen hydrogen peroxide oxidation by the ph value adjusting reaction system
The important channel of ability, but reduce ph value and can bring unsurmountable stability problem for this oxidation reaction again: on the one hand, acid
Property the too strong stability being unfavorable for hydrogen peroxide itself, the decomposition of hydrogen peroxide can be accelerated, on the other hand, ferrous in acid solution
Ion is the stable form of iron, and strengthens with its stability of reduction of ph value it is seen then that acidity is too strong is also unfavorable for that oxidation generates
Iron ion stable existence.
In chemical reaction, product guiding is of paramount importance reaction purpose, so the system generally for bodied ferric sulfate
Standby, can consider to obtain the conversion ratio of ferrous ion as big as possible, thus preparing on the basis of the supply of equal ferrous ion
Obtain more iron ions, so those skilled in the art normally tend to prepare under the conditions of higher ph value (ph ＞ 2) gathering
Close ferric sulfate, but be so unfavorable for the oxidability of hydrogen peroxide.And in the prior art, there is presently no effective technology
How means, to solve above-mentioned contradiction, therefore, formulate rational bodied ferric sulfate synthesis technique with effective control hydrogen peroxide
Decompose, thus reducing the consumption of hydrogen peroxide, improving the oxidation efficiency of hydrogen peroxide, shorten the time of oxidation reaction, be ability
Domain technical barrier urgently to be resolved hurrily.
Content of the invention
What the present invention solved is the technique preparing bodied ferric sulfate in prior art using hydrogen peroxide oxidation process, because of peroxide
Change hydrogen easily decomposes and lead to its oxidation efficiency reduce so that hydrogen peroxide dosage increase, cause production cost increase, produce
Moral character can not reach the problem of primes requirement, and then provides one kind can be prevented effectively from hydrogen peroxide decomposition, improve hydrogen peroxide
Oxidability, and with low cost, be suitable for the preparation method of the bodied ferric sulfate of industrialized production.
The technical scheme that the present invention provides is:
A kind of preparation method of bodied ferric sulfate is it is characterised in that comprise the steps:
(1) using aqueous sulfuric acid, acidification is carried out to ferrous sulfate, obtain the mixed liquor for 0.5-1.5 for the ph value；
(2) at normal temperatures and pressures, the flow channel described mixed liquor and hydrogen peroxide being passed through independently is realized individually flowing
Dynamic reacted with being injected simultaneously in reaction system, the hydrogen peroxide in the ferrous sulfate in described mixed liquor and described hydrogen peroxide
Mol ratio be 1: (0.55-0.7)；
(3) after the reaction of step (2) terminates, described reactant liquor drying and moulding obtains final product ferric polysulfate solid.
In step (1), in described aqueous sulfuric acid, the weight/mass percentage composition of sulfuric acid is 60-70%.
In step (1), described aqueous sulfuric acid is the sulfur waste aqueous acid of generation during Producing Titanium Dioxide；Described sulfuric acid is sub-
Iron is the Waste Sulfuric Acid ferrous iron of generation during Producing Titanium Dioxide, the ferrous sulfate containing more than 90wt% in described Waste Sulfuric Acid ferrous iron.
In step (1), sulfuric acid in ferrous sulfate in described Waste Sulfuric Acid ferrous iron and described sulfur waste aqueous acid mole
Than for 1: (0.25-0.4).
In step (1), the mass concentration of described mixed liquor ferrous ions is 200-250g/l.
In step (2), described mixed liquor and described hydrogen peroxide after respective flow channel flows out, apart from described instead
Answer and contact with each other at bottom portion h height and react, described h height is the 7/10-9/10 of described reactor total height, described
The height of the reactant liquor that mixed liquor is formed after being mixed with described hydrogen peroxide is the 1/2-2/3 of described reactor total height.
In step (2), the flow velocity controlling described hydrogen peroxide is 10-15ml/min.
In step (2), in described hydrogen peroxide, the weight/mass percentage composition of hydrogen peroxide is 25-50%.
In step (2), described reaction system is enclosed system.
In step (2), the ph value of described reaction system reaches and stops reaction during 2-3.
In step (3), the time of described reaction is 1-2 hour；The method of described drying and moulding is mist projection granulating.
The preparation method of bodied ferric sulfate of the present invention, step (1) defines sub- to sulfuric acid using aqueous sulfuric acid
Iron carries out acidification and obtains mixed liquor, and to determine the ph value of this mixed liquor be 0.5-1.5；The present invention is first in polymerised sulphur
Introduce the environment of such strong acid in the preparation process of sour iron, to be conducive to strengthening the oxidability of hydrogen peroxide, improve ferrous from
Son is to the speed of iron ion conversion, and then the time of shortening oxidation reaction, but acidity is too strong and can bring not for this oxidation reaction
Surmountable stability problem: on the one hand, be unfavorable for the stability of hydrogen peroxide itself, the decomposition of hydrogen peroxide can be accelerated, separately
On the one hand, because acid solution ferrous ions are the stable forms of iron, and strengthen with its stability of reduction of ph value, so
The stable existence of the acid too strong iron ion being also unfavorable for oxidation generation.In order to overcome this contradiction, the present inventor passes through a large amount of
Find after research, the independent flowing of flow channel realization that above-mentioned mixed liquor and hydrogen peroxide are passed through independently is injected simultaneously into anti-
Answer in system, ferrous ion can be enable to be fully contacted with hydrogen peroxide and react rapidly, thus being prevented effectively from strong acid ring
The decomposition of the hydrogen peroxide under border, and persistently carrying out with oxidation reaction, the hydrogen ion in reactant liquor is constantly consumed, and enters
And also contribute to strengthen the stability of iron ion, promote oxidation reaction to move to the direction that product generates.And it is of the present invention
Preparation method, step (2) defines that the mol ratio of the hydrogen peroxide in ferrous sulfate in mixed liquor and hydrogen peroxide is 1:
(0.55-0.7), can ensure that ferrous ion is fully converted to iron ion under conditions of this mol ratio, and slightly excessive peroxidating
Hydrogen has no effect on follow-up hydrolysis and polymerisation.
Compared with the preparation method of bodied ferric sulfate of the prior art, the preparation side of bodied ferric sulfate of the present invention
Method has the advantage that
(1) preparation method of bodied ferric sulfate of the present invention, by first mixing aqueous sulfuric acid with ferrous sulfate
Obtain the mixed liquor for 0.5-1.5 for the ph value, then the flow channel that this mixed liquor and hydrogen peroxide are passed through independently is realized individually
Flowing is reacted with being injected simultaneously in reactor, and bodied ferric sulfate is finally obtained；Between the above-mentioned two step of the present invention
Coordinated acts on, and not only facilitates the oxidability strengthening hydrogen peroxide, promotes the speed that ferrous ion converts to iron ion,
Ferrous ion also can be made to be fully contacted with hydrogen peroxide and react rapidly, efficiently solve polyaluminum sulfate of the prior art
The problem that hydrogen peroxide existing for the synthesis technique of iron decomposes under higher temperature or strong acid condition, thus decrease peroxidating
The consumption of hydrogen, reduces cost input, and simplifies operational sequence, substantially reduces the reaction time.Additionally, it is of the present invention
Preparation method is to carry out the reaction such as the oxidation of ferrous sulfate, polymerization, hydrolysis at normal temperatures and pressures, with prior art carry out above-mentioned anti-
Compare for should be required 50-60 DEG C, the equipment of the present invention is simple, simple operation, energy consumption are low, greatly reduces production cost.
The quality of the bodied ferric sulfate obtained by preparation method of the present invention meets gb14591-2006 " water process
Agent: bodied ferric sulfate " specified in Grade A index, and the bodied ferric sulfate being obtained using the present invention processed to waste water
Afterwards, water outlet cod value can stably reach below 86mg/l, so that method of the present invention is suitable for industrialized production.
(2) preparation method of bodied ferric sulfate of the present invention, in mixed liquor with hydrogen peroxide from respective flow channel
After outflow, by the 7/10- making mixed liquor be reactor total height with hydrogen peroxide in the height apart from described reactor bottom
Contact with each other at 9/10, to guarantee that the hydrogen peroxide in the ferrous ion in mixed liquor and hydrogen peroxide is fully contacted and occurs rapidly
Reaction, thus being prevented effectively from the decomposition of hydrogen peroxide, compared with the preparation technology of dropping hydrogen peroxide of the prior art, the present invention
Simplify operational sequence, substantially reduce the reaction time, reduce further production cost.
Additionally, preparation method of the present invention is to carry out in airtight reaction system, even if having in the process
A small amount of hydrogen peroxide decomposes, and oxygen produced by it is also dissolved in reaction system and then promotes the generation of oxidation reaction.
(3) preparation method of bodied ferric sulfate of the present invention, produced during the Producing Titanium Dioxide that can adopt
Sulfur waste aqueous acid and Waste Sulfuric Acid ferrous iron, as reaction raw materials, by comprehensively utilizing to these titanium white by product things, are become
Waste be changed into values, not only can produce huge economic and society benefit, also greatly reduce both titanium white by product thing to land resource
Occupancy volume, reduce environmental pollution, thus being greatly promoted dye industry and the doulbe-sides' victory of Water body cleansing agent industry.
Brief description
Fig. 1 is the xrd spectrogram of the described bodied ferric sulfate that the embodiment of the present invention 1 is obtained.
Specific embodiment
With reference to specific embodiment, the preparation method using bodied ferric sulfate that the present invention provides is described in detail.
In following examples, wt% represents mass percent.
Embodiment 1
The preparation method of the bodied ferric sulfate described in the present embodiment, comprises the steps:
(1) aqueous sulfuric acid that sulfuric acid content is 60wt% is taken to be 91wt% to 2.75kg, ferrous sulfate heptahydrate content
Technical grade green vitriol solid carries out acidification, and stirs and be allowed to be acidified uniformly until obtaining the mixed liquor of ph=1,
The mass concentration of described mixed liquor ferrous ions is 250g/l；
(2) at normal temperatures and pressures, the hydrogen peroxide that described mixed liquor is 25wt% with content of hydrogen peroxide is passed through respectively solely
Vertical flow channel is realized individually flowing, when described mixed liquor and described hydrogen peroxide are after respective flow channel flows out, two
Person is to contact with each other at the 4/5 of reactor total height and react in the height apart from described reactor bottom；Wherein, control
The flow velocity of described mixed liquor is 30ml/min, and the flow velocity of described hydrogen peroxide is 10ml/min so that sulfuric acid in described mixed liquor
Ferrous with described hydrogen peroxide in the mol ratio of hydrogen peroxide be 1: 0.6；
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reactant liquor is in that rufous is thick, and reactant liquor
Ph value reaches 2 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Embodiment 2
The preparation method of the bodied ferric sulfate described in the present embodiment, comprises the steps:
(1) aqueous sulfuric acid that sulfuric acid content is 65wt% is taken to carry out acidification to the ferrous sulfate solid of 2.75kg,
Obtain the mixed liquor of ph=0.5, the mass concentration of described mixed liquor ferrous ions is 200g/l；
(2) at normal temperatures and pressures, the hydrogen peroxide that described mixed liquor is 50wt% with content of hydrogen peroxide is passed through respectively solely
Vertical flow channel is realized individually flowing, when described mixed liquor and described hydrogen peroxide are after respective flow channel flows out, two
Person is to contact with each other at the 7/10 of reactor total height and react in the height apart from described reactor bottom；Wherein, control
The flow velocity making described mixed liquor is 70ml/min, and the flow velocity of described hydrogen peroxide is 10ml/min so that sulphur in described mixed liquor
Acid ferrous with described hydrogen peroxide in the mol ratio of hydrogen peroxide be 1: 0.7；
(3) after the reaction of step (2) carries out 1 hour, after testing, reactant liquor is in that rufous is thick, and the ph of reactant liquor
Value reaches 2.5 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Embodiment 3
The preparation method of the bodied ferric sulfate described in the present embodiment, comprises the steps:
(1) take the aqueous sulfuric acid that sulfuric acid content is 70wt% ferrous to Waste Sulfuric Acid produced during Producing Titanium Dioxide solid
Body 2.75kg carries out acidification, obtains the mixed liquor of ph=1, the mass concentration of described mixed liquor ferrous ions is 220g/
L, the ferrous sulfate containing 90wt% in described Waste Sulfuric Acid ferrous iron solid；
(2) at normal temperatures and pressures, the hydrogen peroxide that described mixed liquor is 37.5wt% with content of hydrogen peroxide is passed through respectively
Independent flow channel is realized individually flowing, when described mixed liquor and described hydrogen peroxide are after respective flow channel flows out,
The two is to contact with each other at the 2/3 of reactor total height and react in the height apart from described reactor bottom；Wherein, control
The flow velocity making described mixed liquor is 61.5ml/min, and the flow velocity of described hydrogen peroxide is 12.5ml/min so that in described mixed liquor
Ferrous sulfate and described hydrogen peroxide in the mol ratio of hydrogen peroxide be 1: 0.65；
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reactant liquor is in that rufous is thick, and reactant liquor
Ph value reaches 2.5 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Embodiment 4
The preparation method of the bodied ferric sulfate described in the present embodiment, comprises the steps:
(1) the sulfur waste aqueous acid producing during taking Producing Titanium Dioxide and Waste Sulfuric Acid ferrous iron solid, using above-mentioned Waste Sulfuric Acid
The aqueous solution carries out acidification to Waste Sulfuric Acid ferrous iron, obtains the mixed liquor of ph=1.5, the quality of described mixed liquor ferrous ions
Concentration is 225g/l；Wherein, the sulfuric acid containing 60wt% in described sulfur waste aqueous acid, contains in described Waste Sulfuric Acid ferrous iron solid
The ferrous sulfate of 92wt%；
(2) at normal temperatures and pressures, the hydrogen peroxide that described mixed liquor is 30wt% with content of hydrogen peroxide is passed through respectively solely
Vertical flow channel is realized individually flowing, when described mixed liquor and described hydrogen peroxide are after respective flow channel flows out, two
Person is to contact with each other at the 4/5 of reactor total height and react in the height apart from described reactor bottom；Wherein, control
The flow velocity of described mixed liquor is 66ml/min, and the flow velocity of described hydrogen peroxide is 15ml/min so that sulfuric acid in described mixed liquor
Ferrous with described hydrogen peroxide in the mol ratio of hydrogen peroxide be 1: 0.55；
(3) after the reaction of step (2) carries out 2 hours, after testing, reactant liquor is in that rufous is thick, and the ph of reactant liquor
Value reaches 3 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Comparative example 1
The preparation method of this comparative example bodied ferric sulfate, comprises the steps:
(1) the technical grade green vitriol solid taking ferrous sulfate heptahydrate content to be 91wt%, be configured to ferrous from
The mass concentration of son is the ferrous sulfate aqueous solution of 250g/l, under being stirred continuously, with the speed of 10ml/min to ferrous sulfate
In the aqueous solution, the hydrogen peroxide for 25wt% for the dropping content of hydrogen peroxide is in rufous to solution；
(2) at normal temperatures and pressures, it is simultaneously added dropwise the hydrogen peroxide that content of hydrogen peroxide is 25wt% in the solution of step (1)
With the aqueous sulfuric acid for 60wt% for the sulfuric acid content, hydrogen peroxide and the rate of addition of aqueous sulfuric acid is controlled to be respectively 10ml/min
And 2ml/min, until ferrous sulfate is 1: 0.6 with the mol ratio of hydrogen peroxide；
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reactant liquor is in that rufous is thick, and reactant liquor
Ph value reaches 2 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Comparative example 2
The preparation method of the bodied ferric sulfate described in this comparative example, comprises the steps:
(1) aqueous sulfuric acid that sulfuric acid content is 60wt% is taken to be 91wt% to 2.75kg, ferrous sulfate heptahydrate content
Technical grade green vitriol solid carries out acidification, and stirs and be allowed to be acidified uniformly until obtaining the mixed liquor of ph=1,
The mass concentration of described mixed liquor ferrous ions is 250g/l；
(2) at normal temperatures and pressures, in the acid-resistant reacting kettle be loaded with described mixed liquor, dropping content of hydrogen peroxide is
The hydrogen peroxide of 25wt% is reacted, and the rate of addition controlling described hydrogen peroxide is 10ml/min, until in described mixed liquor
The mol ratio of the hydrogen peroxide in ferrous sulfate and described hydrogen peroxide is 1: 0.6；
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reactant liquor is in that rufous is thick, and reactant liquor
Ph value reaches 2 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Comparative example 3
The preparation method of the bodied ferric sulfate described in this comparative example, comprises the steps:
(1) at normal temperatures and pressures, sequentially add the industry that ferrous sulfate heptahydrate content is 91wt% in acid-resistant reacting kettle
Level green vitriol solid 3.26kg, content of hydrogen peroxide are the hydrogen peroxide 0.8l of 25wt% and sulfuric acid content is
The aqueous sulfuric acid 0.3l of 60wt%, is reacted being stirred continuously lower mixing, controls the initial ph=1 of reaction mixture, institute
The mol ratio stating the hydrogen peroxide in ferrous sulfate and described hydrogen peroxide is 1: 0.6；
(2) after the reaction of step (2) carries out 1.5 hours, after testing, reactant liquor is in that rufous is thick, and reactant liquor
Ph value reaches 2 and stops reaction, and reactant liquor mist projection granulating obtains faint yellow ferric polysulfate solid.
Comparative example 4
The preparation method of the bodied ferric sulfate described in this comparative example, comprises the steps:
(1) aqueous sulfuric acid that sulfuric acid content is 60wt% is taken to be 91wt% to 2.75kg, ferrous sulfate heptahydrate content
Technical grade green vitriol solid carries out acidification, and stirs and be allowed to be acidified uniformly until obtaining the mixing of ph=2.5
Liquid, the mass concentration of described mixed liquor ferrous ions is 250g/l；
(2) at normal temperatures and pressures, the hydrogen peroxide that described mixed liquor is 25wt% with content of hydrogen peroxide is passed through respectively solely
Vertical flow channel is realized individually flowing, when described mixed liquor and described hydrogen peroxide are after respective flow channel flows out, two
Person is to contact with each other at the 4/5 of reactor total height and react in the height apart from described reactor bottom；Wherein, control
The flow velocity of described mixed liquor is 30ml/min, and the flow velocity of described hydrogen peroxide is 10ml/min so that sulfuric acid in described mixed liquor
Ferrous with described hydrogen peroxide in the mol ratio of hydrogen peroxide be 1: 0.6；
(3), after the reaction of step (2) carries out 1.5 hours, reactant liquor is in that rufous is thick stops reaction, by reactant liquor
Mist projection granulating, obtains faint yellow ferric polysulfate solid.
Experimental example 1
Characterized using the ferric polysulfate solid that X-ray diffraction instrument is obtained to the embodiment of the present invention 1, its xrd spectrogram
As shown in Figure 1.
As seen from Figure 1, in 10-85 ° of sweep limits, obvious crystal peak does not occur, this explanation is according to this
The bodied ferric sulfate basic nodeless mesh degree that bright described method is obtained, the predominantly hydroxide iron sulfate polymer of undefined structure,
And have faint crystal peak between 25-30 °, indicate and be also contaminated with micro crystal.According to above-mentioned analysis, according to this
The bodied ferric sulfate that bright described method is obtained is the hydroxide iron sulfate polymer of the undefined structure being contaminated with micro crystal.
Bodied ferric sulfate method of testing according to specified in gb14591-2006 " water treatment agent: bodied ferric sulfate ", to this
The ferric polysulfate solid that inventive embodiments 1 are obtained carries out performance test, and result is as shown in table 1.
The main performance index of the bodied ferric sulfate that table 1 embodiment 1 is obtained
As shown in Table 1, the liquid of bodied ferric sulfate that the embodiment of the present invention 1 is obtained and solid all meet the finger of Grade A
Mark, this illustrates that the quality of the bodied ferric sulfate that the preparation method of bodied ferric sulfate in accordance with the present invention obtains meets
Grade A index specified in gb14591-2006 " water treatment agent: bodied ferric sulfate ".
Experimental example 2
With the secondary clarifier effluent of certain papermaking enterprise as object, using gathering that embodiment of the present invention 1-4 and comparative example 1-4 are obtained
Close ferric sulfate and carry out wastewater treatment, water treatment efficiency is as shown in table 2.
Water quality contrast before and after table 2 water process
From table 2 it can be seen that being used the bodied ferric sulfate that embodiment of the present invention 1-4 is obtained as water scavengine agent, waste water to be entered
After row is processed, its water outlet cod value can stably reach below 86mg/l.Compared with comparative example 1-4, embodiment of the present invention 1-4 is obtained
Bodied ferric sulfate can significantly reduce the cod value of water outlet, this has absolutely proved and has adopted preparation method of the present invention, that is, first
Ferrous sulfate is carried out with acidification makes its ph=0.5-1.5, then the ferrous sulfate aqueous solution after acidifying is passed through with hydrogen peroxide
Flow channel independently realizes individually flowing to be injected simultaneously into the bodied ferric sulfate tool carrying out in reaction system reacting gained
There is more preferable water treatment efficiency.
Experimental example 3
Using oxygen detection instrument to the oxygen in the acid-resistant reacting kettle described in embodiment of the present invention 1-4 and comparative example 1-4
Burst size is measured, and result is as shown in table 3.
The oxygen emission (mg/l) of table 3 embodiment 1-4 and comparative example 1-4
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Oxygen emission (mg/l) | 106 | 118 | 124 | 120 |
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | |
| Oxygen emission (mg/l) | 508 | 382 | 4010 | 426 |
From table 3 it can be seen that compared with comparative example 1-4, the preparation method described in embodiment of the present invention 1-4 was reacted at it
The amount of the oxygen being discharged in journey is substantially less, and this explanation adopts preparation method of the present invention, first ferrous sulfate is entered
Row acidification makes its ph=0.5-1.5, then by the ferrous sulfate aqueous solution after acidifying and hydrogen peroxide by stream independently
Dynamic passage is realized individually flowing and is reacted with being injected simultaneously in reaction system, can be prevented effectively from the decomposition of hydrogen peroxide, carry
The high oxidation efficiency of hydrogen peroxide, thus substantially reducing production cost, shortening the reaction time so that preparation of the present invention
Method is suitable for industrialization large-scale production.
Obviously, above-described embodiment is only intended to clearly illustrate example, and the not restriction to embodiment.Right
For those of ordinary skill in the art, can also make on the basis of the above description other multi-forms change or
Change.There is no need to be exhaustive to all of embodiment.And the obvious change thus extended out or
Change among still in the protection domain of the invention.
Claims (10)
1. a kind of preparation method of bodied ferric sulfate is it is characterised in that comprise the steps:
(1) using aqueous sulfuric acid, acidification is carried out to ferrous sulfate, obtain the mixed liquor for 0.5-1.5 for the ph value；
(2) at normal temperatures and pressures, the flow channel described mixed liquor and hydrogen peroxide being passed through independently realize individually flowing with
It is injected simultaneously in reaction system and reacted, the rubbing of the hydrogen peroxide in the ferrous sulfate in described mixed liquor and described hydrogen peroxide
That ratio is 1:(0.55-0.7)；
(3) after the reaction of step (2) terminates, reactant liquor drying and moulding obtains final product ferric polysulfate solid；
In step (2), described mixed liquor and described hydrogen peroxide after respective flow channel flows out, apart from reactor bottom
Contact with each other at h height and react, described h height is the 7/10-9/10 of described reactor total height, described mixed liquor with
The height of the reactant liquor being formed after described hydrogen peroxide mixing is the 1/2-2/3 of described reactor total height.
2. the preparation method of bodied ferric sulfate according to claim 1 is it is characterised in that in step (1), described sulfuric acid water
In solution, the weight/mass percentage composition of sulfuric acid is 60-70%.
3. the preparation method of bodied ferric sulfate according to claim 2 is it is characterised in that in step (1), described sulfuric acid water
Solution is the sulfur waste aqueous acid of generation during Producing Titanium Dioxide；Described ferrous sulfate is the sulfur waste of generation during Producing Titanium Dioxide
Acid is ferrous, the ferrous sulfate containing more than 90wt% in described Waste Sulfuric Acid ferrous iron.
4. the preparation method of bodied ferric sulfate according to claim 1 is it is characterised in that in step (1), described mixed liquor
The mass concentration of ferrous ions is 200-250g/l.
5. the preparation method of bodied ferric sulfate according to claim 1 is it is characterised in that in step (2), control described double
The flow velocity of oxygen water is 10-15ml/min.
6. the preparation method of bodied ferric sulfate according to claim 5 is it is characterised in that in step (2), described hydrogen peroxide
The weight/mass percentage composition of middle hydrogen peroxide is 25-50%.
7. the preparation method according to the arbitrary described bodied ferric sulfate of claim 1-6 is it is characterised in that in step (2), described
The ph value of reaction system reaches and stops reaction during 2-3.
8. the preparation method of the bodied ferric sulfate according to any one of claim 1-6 is it is characterised in that in step (2), institute
Stating reaction system is enclosed system.
9. the preparation method of bodied ferric sulfate according to claim 7 is it is characterised in that in step (2), described reactant
It is for enclosed system.
10. the preparation method of the bodied ferric sulfate according to claim 1,2,3,4,5,6 or 9 is it is characterised in that step
(3), in, the time of described reaction is 1-2 hour；The method of described drying and moulding is mist projection granulating.
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| CN107417025A (en) * | 2017-08-10 | 2017-12-01 | 西安瑞联新材料股份有限公司 | A kind of processing method of folic acid sulfur waste sour water |
| CN108046335B (en) * | 2017-11-29 | 2020-06-12 | 兰州理工大学白银新材料研究院 | Preparation method of solid polymeric ferric sulfate |
| CN108163901A (en) * | 2018-01-02 | 2018-06-15 | 张家港洁利环保科技有限公司 | Production method is added dropwise in Polyferric Sulfate industry |
| CN110240241A (en) * | 2018-03-09 | 2019-09-17 | 天津大学 | A kind of preparation method of high dispersive amorphous polymer ferric sulfate |
| 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 |
| CN109928474B (en) * | 2019-04-15 | 2020-11-03 | 常州纺织服装职业技术学院 | Method for preparing polymeric ferric sulfate from waste sulfuric acid containing o-cyano-p-nitroaniline and application |
| CN111218218B (en) * | 2019-12-02 | 2022-01-18 | 湖南利农五倍子产业发展有限公司 | Method for producing shoe polish by using wastewater from gallic acid production |
| CN111675246A (en) * | 2020-06-30 | 2020-09-18 | 河南爱尔福克化学股份有限公司 | Method for preparing polymeric ferric sulfate from ferrous mother liquor of titanium dioxide byproduct |
| CN112028133B (en) * | 2020-10-13 | 2022-12-20 | 马鞍山健鼎化工有限公司 | Preparation method of polymeric ferric sulfate |
| CN112479263B (en) * | 2020-12-29 | 2022-08-09 | 湖南金化科技集团有限公司 | Method for producing polymeric ferric sulfate |
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