CN104692467A - Preparation method of polyferric sulfate - Google Patents
Preparation method of polyferric sulfate Download PDFInfo
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- CN104692467A CN104692467A CN201510080038.9A CN201510080038A CN104692467A CN 104692467 A CN104692467 A CN 104692467A CN 201510080038 A CN201510080038 A CN 201510080038A CN 104692467 A CN104692467 A CN 104692467A
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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 grown up the eighties in 20th century, and its liquid is the sticky shape of reddish-brown, and solid is then faint yellow unformed powder, very easily water-soluble, can be configured to the solution of any concentration.With traditional flocculation agent as compared with iron trichloride, Tai-Ace S 150, chloro sulphuric acid iron, aluminium chlorohydroxide etc., bodied ferric sulfate has the advantages such as the pH value range that production cost is low, scavenging process is adding less, adapt to water body is wide, impurity (COD, heavy metal, suspended substance etc.) clearance is high, debris concentration is low, alumina blossom particles is large, settling velocity is fast, good decolorizing effect, is widely used in the purifying treatment of the water bodys such as Drinking Water, process water, municipal effluent and trade effluent.
At present, the preparation technology for bodied ferric sulfate mainly contains direct oxidation method and catalytic oxidation.The preparation of most of bodied ferric sulfate adopts direct oxidation method, namely adds oxygenant (H in process of production
2o
2, KClO
3, HNO
3deng) carrying out oxide treatment, this method operational path is comparatively simple, can reduce facility investment and production link for industrial production, thus reduces production cost.Wherein, the production technique of Potcrate oxidation style is simple, reaction efficiency is high, good without atmospheric pollution, product stability, and coagulating agent and sterilant can be doubled as containing oxymuriate in product, but because remaining the chlorion of high level and chloranion and being unsuitable for drinking water treatment in goods, and Potcrate is expensive, cause product cost high, be unfavorable for suitability for industrialized production; The cost of nitric acid oxidation method is lower, and product concentration is high, easily makes solid-state product, but the NO generated in reaction
2pollute the environment, need device for absorbing tail gas be increased; And hydrogen peroxide oxidation process produces the technique of bodied ferric sulfate, because hydrogen peroxide is a kind of strong oxidizer under sour environment, its reduzate only has water, both pollutent had not been had not have the generation of solid waste yet, and equipment is simple, with short production cycle, product stability is good, thus hydrogen peroxide obtains increasing favor as a kind of oxygenant of environmental protection, and the technique adopting hydrogen peroxide method to produce bodied ferric sulfate is also extremely praised highly.
The technique collection oxidation of hydrogen peroxide method production bodied ferric sulfate, hydrolysis, polymerization three react in an individual system, and wherein, oxidizing reaction is that the rate determining step of this series reaction is rapid, and its reaction equation is as follows:
2FcSO
4+H
2O
2+H
2SO
4＝Fe
2(SO
4)
3+2H
2O
In above-mentioned oxidation reaction process, the factor of the speed and yield that affect this reaction is many-sided, comprise the consumption of hydrogen peroxide, the consumption of sulfuric acid, temperature of reaction, pH value, order of addition(of ingredients) etc., to the analysis of above-mentioned influence factor " test of bodied ferric sulfate synthesis and property " (" Progress & New Products " people such as Liu Zhirong, 17th volume the 8th phase 35-37 page in 2003) in a literary composition by detailed record, they pass through hydrogen peroxide consumption, oxidizing temperature, the factors such as the consumption of the vitriol oil and feed postition carry out investigating rear discovery, the feed postition of the vitriol oil is the weight factor affecting the reaction times, reaction is adopted to drip sulphate method mid-term, and control a certain amount of flow velocity reaction is carried out under pH value (pH > 2) high as far as possible, thus make Fe
2+be oxidized to Fe
3+speed greatly accelerate, reaction times corresponding shortening, significantly improves efficiency, and determine the best processing route producing bodied ferric sulfate on this basis: namely at normal temperatures and pressures, in the container of iron vitriol and water, under constantly stirring, first dripping hydrogen peroxide to solution with certain flow rate be reddish-brown, then while drip quantitative hydrogen peroxide and the vitriol oil until react complete with different in flow rate.
Although the bodied ferric sulfate that above-mentioned synthesis technique obtains is better to the flocculating effect of aqueous suspension ofkaolin, its Fe
3+content but fail to reach first grade requirement, this is because, above-mentioned technique first instills in the aqueous solution of ferrous sulfate by hydrogen peroxide, and the pH value of this aqueous solution is about 3.7, under this pH value environment, the oxidation capacity of hydrogen peroxide is more weak, and is unfavorable for carrying out rapidly of oxidizing reaction, thus the hydrogen peroxide not participating in reaction is in time decomposed; Because of this technique, also the phase adds the vitriol oil in the reaction again, can a large amount of heat release when it mixes with water, not only further promotes the decomposition of hydrogen peroxide, also may cause security incident.As can be seen here, above-mentioned existing processing condition cannot avoid the decomposition of hydrogen peroxide, the oxidation efficiency of hydrogen peroxide is reduced, thus increases the dosage of hydrogen peroxide, not only cause the increase of production cost, also dilute reaction solution, cause the Fe in product
3+content fails to reach the requirement of first grade.If solved the problem, so just need the oxidation capacity improving hydrogen peroxide in reaction process as far as possible, by the important channel that the pH value of adjustment reaction system is enhancing hydrogen peroxide oxidation ability, but reduce pH value and can bring unsurmountable stability problem for this oxidizing reaction again: on the one hand, the acid stability being unfavorable for excessively by force hydrogen peroxide self, the decomposition of hydrogen peroxide can be accelerated, on the other hand, acidic solution ferrous ions is the most stable form of iron, and strengthen with its stability of reduction of pH value, visible, the acid stable existence crossing the iron ion being also unfavorable for by force oxidation generation.
In chemical reaction, product guiding is of paramount importance reaction object, so generally for the preparation of bodied ferric sulfate, the transformation efficiency obtaining ferrous ion large as far as possible can be considered, thus more iron ion is prepared on the supply basis of equal ferrous ion, so those skilled in the art tend to prepare bodied ferric sulfate usually under higher pH value (pH > 2) condition, but be unfavorable for the oxidation capacity of hydrogen peroxide like this.And in the prior art, effective technique means is not also had to solve above-mentioned contradiction at present, therefore, how to formulate rational bodied ferric sulfate synthesis technique effectively to control the decomposition of hydrogen peroxide, thus reduce over hydrogen oxide consumption, improve hydrogen peroxide oxidation efficiency, shorten time of oxidizing reaction, be this area technical barrier urgently to be resolved hurrily.
Summary of the invention
What the present invention solved is the technique adopting hydrogen peroxide oxidation process to prepare bodied ferric sulfate in prior art, its oxidation efficiency is caused to reduce because hydrogen peroxide is easy to decompose, the dosage of hydrogen peroxide is increased, cause the problem that production cost increases, product performance do not reach first grade requirement, and then a kind of oxidation capacity effectively can avoided peroxide decomposition, improve hydrogen peroxide is provided, and with low cost, be suitable for the preparation method of the bodied ferric sulfate of suitability for industrialized production.
Technical scheme provided by the invention is:
A preparation method for bodied ferric sulfate, is characterized in that, comprises the steps:
(1) use aqueous sulfuric acid to carry out acidification to ferrous sulfate, obtain the mixed solution that pH value is 0.5-1.5;
(2) at normal temperatures and pressures, described mixed solution and hydrogen peroxide are realized independent flowing by flow passage independently to react to inject reaction system simultaneously, the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide is 1: (0.55-0.7);
(3) after the reaction of step (2) terminates, by described reaction solution drying and moulding, ferric polysulfate solid is obtained.
In step (1), in described aqueous sulfuric acid, the mass percentage of sulfuric acid is 60-70%.
In step (1), described aqueous sulfuric acid is the Waste Sulfuric Acid aqueous solution produced in Producing Titanium Dioxide process; Described ferrous sulfate is that the Waste Sulfuric Acid produced in Producing Titanium Dioxide process is ferrous, the ferrous sulfate containing more than 90wt% in described Waste Sulfuric Acid ferrous iron.
In step (1), the mol ratio of the sulfuric acid in the ferrous sulfate in described Waste Sulfuric Acid ferrous iron and the described Waste Sulfuric Acid aqueous solution is 1: (0.25-0.4).
In step (1), the mass concentration of described mixed solution ferrous ions is 200-250g/L.
In step (2), described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, contacting with each other apart from H At The Height bottom described reactor and reacting, described H is highly the 7/10-9/10 of described reactor total height, and the height of the reaction solution formed after described mixed solution mixes 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 mass percentage of hydrogen peroxide is 25-50%.
In step (2), described reaction system is enclosed system.
In step (2), the stopped reaction when pH value of described reaction system reaches 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 and uses aqueous sulfuric acid to carry out acidification to ferrous sulfate and obtain mixed solution, and the pH value determining this mixed solution is 0.5-1.5, the present invention introduces the environment of strong acid like this first in the preparation process of bodied ferric sulfate, to be conducive to the oxidation capacity strengthening hydrogen peroxide, improve the speed that ferrous ion transforms to iron ion, and then shorten the time of oxidizing reaction, but acid mistake can bring unsurmountable stability problem for this oxidizing reaction again by force: on the one hand, be unfavorable for the stability of hydrogen peroxide self, the decomposition of hydrogen peroxide can be accelerated, on the other hand, due to the most stable form that acidic solution ferrous ions is iron, and strengthen with its stability of reduction of pH value, the stable existence being also unfavorable for by force being oxidized the iron ion generated is crossed so acid.In order to overcome this contradiction, the present inventor is by finding after large quantity research, above-mentioned mixed solution and hydrogen peroxide are realized flowing to inject reaction system separately by flow passage independently simultaneously, ferrous ion can be enable fully to contact with hydrogen peroxide and react rapidly, thus effectively avoid the decomposition of the hydrogen peroxide under strong acid environment, and along with oxidizing reaction continue carry out, hydrogen ion in reaction solution is constantly consumed, and then also contributing to the stability strengthening iron ion, the direction that promotion oxidizing reaction generates to product is moved.And preparation method of the present invention, the mol ratio that step (2) defines the ferrous sulfate in mixed solution and the hydrogen peroxide in hydrogen peroxide is 1: (0.55-0.7), can guarantee that under the condition of this mol ratio ferrous ion is converted into iron ion completely, and not affect follow-up hydrolysis and polyreaction little over the hydrogen peroxide of amount.
Compared with the preparation method of bodied ferric sulfate of the prior art, preparation method's tool of bodied ferric sulfate of the present invention has the following advantages:
(1) preparation method of bodied ferric sulfate of the present invention, by first aqueous sulfuric acid and ferrous sulfate being mixed to get the mixed solution that pH value is 0.5-1.5, again this mixed solution and hydrogen peroxide are realized flowing separately by flow passage independently and to react to inject reactor simultaneously, finally obtain bodied ferric sulfate; Coordinated effect between above-mentioned two steps of the present invention, not only contribute to the oxidation capacity strengthening hydrogen peroxide, promote the speed that ferrous ion transforms to iron ion, ferrous ion also can be made fully to contact with hydrogen peroxide and react rapidly, the problem that the hydrogen peroxide existing for synthesis technique efficiently solving bodied ferric sulfate of the prior art decomposes under comparatively high temps or strong acid condition, thus decrease the consumption of hydrogen peroxide, reduce cost to drop into, and simplify operation sequence, substantially reduce the reaction times.In addition, preparation method of the present invention carries out the reaction such as oxidation, polymerization, hydrolysis of ferrous sulfate at normal temperatures and pressures, compared with 50-60 DEG C that carries out needed for above-mentioned reaction with prior art, 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 the acceptable end product index of regulation in GB14591-2006 " water conditioner: bodied ferric sulfate ", and after using the bodied ferric sulfate that obtains of the present invention to process waste water, water outlet COD value can be stablized and reaches below 86mg/L, thus makes method of the present invention be suitable for suitability for industrialized production.
(2) preparation method of bodied ferric sulfate of the present invention, at mixed solution and hydrogen peroxide from after respective flow passage flows out, contact with each other by making mixed solution and 7/10-9/10 place that hydrogen peroxide apart from the height bottom described reactor is being reactor total height, to guarantee that the ferrous ion in mixed solution fully contacts with the hydrogen peroxide in hydrogen peroxide and reacts rapidly, thus effectively avoid the decomposition of hydrogen peroxide, compared with the preparation technology of dropping hydrogen peroxide of the prior art, this invention simplifies operation sequence, substantially reduce the reaction times, reduce further production cost.
In addition, preparation method of the present invention carries out in airtight reaction system, even if there is a small amount of peroxide decomposition in the process, its oxygen produced is also by the generation being dissolved in reaction system and then accelerating oxidation reacts.
(3) preparation method of bodied ferric sulfate of the present invention, the Waste Sulfuric Acid aqueous solution produced in the Producing Titanium Dioxide process that can adopt and Waste Sulfuric Acid ferrous iron are as reaction raw materials, by fully utilizing these titanium white by product things, turned waste into wealth, not only can produce huge economic and society benefit, also greatly reduce both titanium white by product thing to the occupancy volume of land resources, reduce environmental pollution, thus greatly facilitate the doulbe-sides' victory of dyestuffs industries and Water body cleansing agent industry.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the described bodied ferric sulfate that the embodiment of the present invention 1 obtains.
Embodiment
Below in conjunction with specific embodiment, the preparation method of bodied ferric sulfate that utilizes provided by the invention 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) getting sulfuric acid content is that the aqueous sulfuric acid of 60wt% carries out acidification to the technical grade ferrous sulfate solid that 2.75Kg, iron vitriol content are 91wt%, and stirring makes it acidifying evenly until obtain the mixed solution of pH=1, the mass concentration of described mixed solution ferrous ions is 250g/L;
(2) at normal temperatures and pressures, be that the hydrogen peroxide of 25wt% realizes flowing separately by flow passage independently by described mixed solution and content of hydrogen peroxide, when described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, 4/5 place that the two apart from the height bottom described reactor is being reactor total height contacts with each other and reacts; Wherein, the flow velocity controlling described mixed solution is 30mL/min, and the flow velocity of described hydrogen peroxide is 10mL/min, makes the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide be 1: 0.6;
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2 i.e. stopped reaction, by reaction solution 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) getting sulfuric acid content is that the ferrous sulfate solid of aqueous sulfuric acid to 2.75Kg of 65wt% carries out acidification, and obtain the mixed solution of pH=0.5, the mass concentration of described mixed solution ferrous ions is 200g/L;
(2) at normal temperatures and pressures, be that the hydrogen peroxide of 50wt% realizes flowing separately by flow passage independently by described mixed solution and content of hydrogen peroxide, when described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, 7/10 place that the two apart from the height bottom described reactor is being reactor total height contacts with each other and reacts; Wherein, the flow velocity controlling described mixed solution is 70mL/min, and the flow velocity of described hydrogen peroxide is 10mL/min, makes the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide be 1: 0.7;
(3) after the reaction of step (2) carries out 1 hour, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2.5 i.e. stopped reaction, by reaction solution 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) get the aqueous sulfuric acid that sulfuric acid content is 70wt% and acidification is carried out to the ferrous solid 2.75Kg of the Waste Sulfuric Acid produced in Producing Titanium Dioxide process, obtain the mixed solution of pH=1, the mass concentration of described mixed solution ferrous ions is 220g/L, the ferrous sulfate containing 90wt% in the ferrous solid of described Waste Sulfuric Acid;
(2) at normal temperatures and pressures, be that the hydrogen peroxide of 37.5wt% realizes flowing separately by flow passage independently by described mixed solution and content of hydrogen peroxide, when described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, 2/3 place that the two apart from the height bottom described reactor is being reactor total height contacts with each other and reacts; Wherein, the flow velocity controlling described mixed solution is 61.5mL/min, and the flow velocity of described hydrogen peroxide is 12.5mL/min, makes the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide be 1: 0.65;
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2.5 i.e. stopped reaction, by reaction solution 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 Waste Sulfuric Acid aqueous solution and the ferrous solid of Waste Sulfuric Acid that produce in Producing Titanium Dioxide process is got, the above-mentioned Waste Sulfuric Acid aqueous solution is used to carry out acidification to Waste Sulfuric Acid ferrous iron, obtain the mixed solution of pH=1.5, the mass concentration of described mixed solution ferrous ions is 225g/L; Wherein, the sulfuric acid containing 60wt% in the described Waste Sulfuric Acid aqueous solution, the ferrous sulfate containing 92wt% in the ferrous solid of described Waste Sulfuric Acid;
(2) at normal temperatures and pressures, be that the hydrogen peroxide of 30wt% realizes flowing separately by flow passage independently by described mixed solution and content of hydrogen peroxide, when described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, 4/5 place that the two apart from the height bottom described reactor is being reactor total height contacts with each other and reacts; Wherein, the flow velocity controlling described mixed solution is 66mL/min, and the flow velocity of described hydrogen peroxide is 15mL/min, makes the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide be 1: 0.55;
(3) after the reaction of step (2) carries out 2 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 3 i.e. stopped reaction, by reaction solution 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 ferrous sulfate solid that iron vitriol content is 91wt% is got, the mass concentration being mixed with ferrous ion is the ferrous sulfate aqueous solution of 250g/L, under constantly stirring, in ferrous sulfate aqueous solution, dripping with the speed of 10mL/min hydrogen peroxide to the solution that content of hydrogen peroxide is 25wt% is reddish-brown;
(2) at normal temperatures and pressures, drip the hydrogen peroxide that content of hydrogen peroxide is 25wt% and sulfuric acid content is the aqueous sulfuric acid of 60wt% in the solution of step (1) simultaneously, the rate of addition controlling hydrogen peroxide and aqueous sulfuric acid is respectively 10mL/min and 2mL/min, until the mol ratio of ferrous sulfate and hydrogen peroxide is 1: 0.6;
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2 i.e. stopped reaction, by reaction solution 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) getting sulfuric acid content is that the aqueous sulfuric acid of 60wt% carries out acidification to the technical grade ferrous sulfate solid that 2.75Kg, iron vitriol content are 91wt%, and stirring makes it acidifying evenly until obtain the mixed solution of pH=1, the mass concentration of described mixed solution ferrous ions is 250g/L;
(2) at normal temperatures and pressures, in the acid-resistant reacting kettle being loaded with described mixed solution, drip content of hydrogen peroxide is that the hydrogen peroxide of 25wt% reacts, the rate of addition controlling described hydrogen peroxide is 10mL/min, until the mol ratio of the ferrous sulfate in described mixed solution and the hydrogen peroxide in described hydrogen peroxide is 1: 0.6;
(3) after the reaction of step (2) carries out 1.5 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2 i.e. stopped reaction, by reaction solution 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, in acid-resistant reacting kettle, add technical grade ferrous sulfate solid 3.26Kg that iron vitriol content is 91wt% successively, aqueous sulfuric acid 0.3L that hydrogen peroxide 0.8L that content of hydrogen peroxide is 25wt% and sulfuric acid content are 60wt%, mix under constantly stirring and react, control the initial pH=1 of reaction mixture, the mol ratio of the hydrogen peroxide in described ferrous sulfate and described hydrogen peroxide is 1: 0.6;
(2) after the reaction of step (2) carries out 1.5 hours, after testing, reaction solution is that reddish-brown is thick, and the pH value of reaction solution reaches 2 i.e. stopped reaction, by reaction solution 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) getting sulfuric acid content is that the aqueous sulfuric acid of 60wt% carries out acidification to the technical grade ferrous sulfate solid that 2.75Kg, iron vitriol content are 91wt%, and stirring makes it acidifying evenly until obtain the mixed solution of pH=2.5, the mass concentration of described mixed solution ferrous ions is 250g/L;
(2) at normal temperatures and pressures, be that the hydrogen peroxide of 25wt% realizes flowing separately by flow passage independently by described mixed solution and content of hydrogen peroxide, when described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, 4/5 place that the two apart from the height bottom described reactor is being reactor total height contacts with each other and reacts; Wherein, the flow velocity controlling described mixed solution is 30mL/min, and the flow velocity of described hydrogen peroxide is 10mL/min, makes the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide be 1: 0.6;
(3), after the reaction of step (2) carries out 1.5 hours, reaction solution is the thick i.e. stopped reaction of reddish-brown, by reaction solution mist projection granulating, obtains faint yellow ferric polysulfate solid.
Experimental example 1
The ferric polysulfate solid adopting x-ray diffractometer obtained to the embodiment of the present invention 1 characterizes, and its XRD spectra as shown in Figure 1.
As seen from Figure 1, obvious crystal peak is there is not in the sweep limit of 10-85 °, this illustrates according to the obtained basic nodeless mesh degree of bodied ferric sulfate of method of the present invention, be mainly the hydroxide iron sulfate polymkeric substance of undefined structure, and between 25-30 °, have faint crystal peak, indicating also to mix has micro-crystal.According to above-mentioned analysis, the bodied ferric sulfate obtained according to method of the present invention is the hydroxide iron sulfate polymkeric substance mixing the undefined structure having micro-crystal.
According to the bodied ferric sulfate testing method of regulation in GB14591-2006 " water conditioner: bodied ferric sulfate ", the ferric polysulfate solid obtained to the embodiment of the present invention 1 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 the bodied ferric sulfate that the embodiment of the present invention 1 is obtained and solid all meet the index of acceptable end product, and this illustrates that the quality of the bodied ferric sulfate that the preparation method according to bodied ferric sulfate of the present invention obtains meets the acceptable end product index of regulation in GB14591-2006 " water conditioner: bodied ferric sulfate ".
Experimental example 2
With the secondary clarifier effluent of certain papermaking enterprise for object, adopt the obtained bodied ferric sulfate of embodiment of the present invention 1-4 and comparative example 1-4 to carry out wastewater treatment, water treatment efficiency is as shown in table 2.
Water quality contrast before and after table 2 water treatment
As can be seen from Table 2, after using the obtained bodied ferric sulfate of embodiment of the present invention 1-4 to process waste water as water scavengine agent, its water outlet COD value can be stablized and reaches below 86mg/L.Compared with comparative example 1-4, the bodied ferric sulfate that embodiment of the present invention 1-4 obtains significantly can reduce the COD value of water outlet, this has absolutely proved employing preparation method of the present invention, namely first acidification is carried out to ferrous sulfate and make its pH=0.5-1.5, then the ferrous sulfate aqueous solution after acidifying and hydrogen peroxide are realized the independent bodied ferric sulfate carrying out reacting gained to inject reaction system simultaneously that flows by flow passage independently there is better water treatment efficiency.
Experimental example 3
Adopt oxygen detection instrument to measure the oxygen emission in the acid-resistant reacting kettle described in embodiment of the present invention 1-4 and comparative example 1-4, 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 |
As can be seen from Table 3, compared with comparative example 1-4, the amount of the oxygen that the preparation method described in embodiment of the present invention 1-4 discharges in its reaction process is obviously less, this illustrates and adopts preparation method of the present invention, namely first acidification is carried out to ferrous sulfate and make its pH=0.5-1.5, again the ferrous sulfate aqueous solution after acidifying and hydrogen peroxide are realized independent flowing by flow passage independently to react to inject reaction system simultaneously, effectively can avoid the decomposition of hydrogen peroxide, improve the oxidation efficiency of hydrogen peroxide, thus greatly reduce production cost, Reaction time shorten, preparation method of the present invention is made to be suitable for industrialization scale operation.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a preparation method for bodied ferric sulfate, is characterized in that, comprises the steps:
(1) use aqueous sulfuric acid to carry out acidification to ferrous sulfate, obtain the mixed solution that pH value is 0.5-1.5;
(2) at normal temperatures and pressures, described mixed solution and hydrogen peroxide are realized independent flowing by flow passage independently to react to inject reaction system simultaneously, the mol ratio of the hydrogen peroxide in the ferrous sulfate in described mixed solution and described hydrogen peroxide is 1: (0.55-0.7);
(3) after the reaction of step (2) terminates, by reaction solution drying and moulding, ferric polysulfate solid is obtained.
2. the preparation method of bodied ferric sulfate according to claim 1, is characterized in that, in step (1), in described aqueous sulfuric acid, the mass percentage of sulfuric acid is 60-70%.
3. the preparation method of bodied ferric sulfate according to claim 1 and 2, is characterized in that, in step (1), described aqueous sulfuric acid is the Waste Sulfuric Acid aqueous solution produced in Producing Titanium Dioxide process; Described ferrous sulfate is that the Waste Sulfuric Acid produced in Producing Titanium Dioxide process is ferrous, the ferrous sulfate containing more than 90wt% in described Waste Sulfuric Acid ferrous iron.
4., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-3, it is characterized in that, in step (1), the mass concentration of described mixed solution ferrous ions is 200-250g/L.
5. according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-4, it is characterized in that, in step (2), described mixed solution and described hydrogen peroxide are from after respective flow passage flows out, bottom distance reactor, H At The Height contacts with each other and reacts, described H is highly the 7/10-9/10 of described reactor total height, and the height of the reaction solution formed after described mixed solution mixes with described hydrogen peroxide is the 1/2-2/3 of described reactor total height.
6., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-5, it is characterized in that, in step (2), the flow velocity controlling described hydrogen peroxide is 10-15mL/min.
7., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-6, it is characterized in that, in step (2), in described hydrogen peroxide, the mass percentage of hydrogen peroxide is 25-50%.
8., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-7, it is characterized in that, in step (2), the stopped reaction when pH value of described reaction system reaches 2-3.
9., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-8, it is characterized in that, in step (2), described reaction system is enclosed system.
10., according to the preparation method of the arbitrary described bodied ferric sulfate of claim 1-9, it is characterized in that, in step (3), the time of described reaction is 1-2 hour; The method of described drying and moulding is mist projection granulating.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN105542776A (en) * | 2015-12-18 | 2016-05-04 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
| 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 |
| CN108046335A (en) * | 2017-11-29 | 2018-05-18 | 兰州理工大学白银新材料研究院 | A kind of solid ferric polysulfate preparation method |
| 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 |
| 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 |
| CN109928474A (en) * | 2019-04-15 | 2019-06-25 | 常州纺织服装职业技术学院 | The methods and applications of bodied ferric sulfate are prepared with the Waste Sulfuric Acid containing adjacent cyano paranitroanilinum |
| CN110240241A (en) * | 2018-03-09 | 2019-09-17 | 天津大学 | A kind of preparation method of high dispersive amorphous polymer ferric sulfate |
| CN111218218A (en) * | 2019-12-02 | 2020-06-02 | 湖南康倍奇生物科技有限公司 | 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 |
| CN112028133A (en) * | 2020-10-13 | 2020-12-04 | 马鞍山健鼎化工有限公司 | Preparation method of polymeric ferric sulfate |
| CN112479263A (en) * | 2020-12-29 | 2021-03-12 | 湖南金化科技集团有限公司 | Method for producing polymeric ferric sulfate |
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Cited By (16)
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| CN105542776A (en) * | 2015-12-18 | 2016-05-04 | 北京高能时代环境技术股份有限公司 | Stabilizing agent for harmless treatment of arsenic-contaminated soil |
| 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 |
| CN108046335A (en) * | 2017-11-29 | 2018-05-18 | 兰州理工大学白银新材料研究院 | A kind of solid ferric polysulfate preparation method |
| 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 |
| CN109928474A (en) * | 2019-04-15 | 2019-06-25 | 常州纺织服装职业技术学院 | The methods and applications of bodied ferric sulfate are prepared with the Waste Sulfuric Acid containing adjacent cyano paranitroanilinum |
| 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 |
| CN111218218A (en) * | 2019-12-02 | 2020-06-02 | 湖南康倍奇生物科技有限公司 | Method for producing shoe polish by using wastewater from gallic acid production |
| 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 |
| CN112028133A (en) * | 2020-10-13 | 2020-12-04 | 马鞍山健鼎化工有限公司 | Preparation method of polymeric ferric sulfate |
| 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 |
| CN112479263A (en) * | 2020-12-29 | 2021-03-12 | 湖南金化科技集团有限公司 | Method for producing 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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