CN100537441C - Aluminum sulfate, production method for aluminum sulfate and its uses - Google Patents
Aluminum sulfate, production method for aluminum sulfate and its uses Download PDFInfo
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- CN100537441C CN100537441C CNB2006101630988A CN200610163098A CN100537441C CN 100537441 C CN100537441 C CN 100537441C CN B2006101630988 A CNB2006101630988 A CN B2006101630988A CN 200610163098 A CN200610163098 A CN 200610163098A CN 100537441 C CN100537441 C CN 100537441C
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Abstract
A method of the present invention, aluminum sulfate can be efficiently and commercially advantageously prepared. This production method for aluminum sulfate is characterized by reacting sulfuric acid with aluminum hydroxide in the presence of nitric acid based on a reaction system.
Description
The application is that application number is 02150581.0, the applying date is on November 21st, 2002, denomination of invention is divided an application for the patent application of " Tai-Ace S 150, Its Preparation Method And Use ".
Technical field
The present invention relates to waste water conditioner, method of wastewater treatment and use the device of this waste water conditioner.
Background technology
Tai-Ace S 150 is drainge treating agent (inorganic flocculant) use as sewage, plant drainage or last water etc., perhaps as paper cementing agent, leather retanning agent or widely used industrial pharmaceutical chemicalss such as greasy finings, various catalyzer.
This Tai-Ace S 150 is usually by following method preparation, promptly in the reactive tank heat-resisting, that the acid resistance material constitutes, add sulfuric acid, heat to wherein dropping into aluminium hydroxide, the dense alum liquor that dilute with water obtains in reactive tank, store, the cooling back is adjusted concentration and is made product (spy opens clear 54-106098, special fair 7-25541).
But, adopt this method in the past, must be heated to about 100～130 ℃, and tens of minutes to 2 hours curing time must be arranged.Perhaps react with promotion by high density (90～98 weight %) sulfuric acid that uses the reagent level.Usually, be about 70～90 weight % by vitriolic concentration in the sulfur waste acid of semiconductor factory's discharge, therefore effectively utilize and be somebody's turn to do useless vitriolic occasion in consideration, hope occurs can be by the method for low-concentration sulfuric acid efficient production Tai-Ace S 150.
In addition, when Tai-Ace S 150 is used as above-mentioned discharge treatment agent, with other treatment agents, for example PAC (polymerize aluminum chloride) compares, and does not add pharmaceutical chemicals in a large number if exist, then can not obtain the problem of the aggegation speed that satisfy, therefore in recent years, the situation that Tai-Ace S 150 is replaced to PAC increases, because Tai-Ace S 150 can use sulfuric acid waste as raw material, thereby from the viewpoint of efficent use of resources (saving resource), present situation is to thirst for having the agglutinating performance equal or above with PAC.
The object of the present invention is to provide a kind of sulfuric acid, particularly do not need heating source, simultaneously at low temperature and can efficient in the short period of time prepare the method for Tai-Ace S 150 well by lower concentration.
In addition, the object of the present invention is to provide a kind of ratio Tai-Ace S 150 in the past good and have a composition that contains Tai-Ace S 150 of the agglutinating performance identical or above with PAC.
Solve the method for problem
The inventor to achieve these goals, through concentrated research repeatedly, the result is surprised to find that by sulfuric acid and preparation of aluminium hydroxide Tai-Ace S 150 the time, can promote reaction by having nitric acid or aqueous hydrogen peroxide solution, further the present invention has been finished in research repeatedly finally.
And the inventor studies through concentrating one's attention on repeatedly to achieve these goals, and the result is surprised to find that can improve agglutinating performance by the nitric acid that coexists in Tai-Ace S 150, and further the present invention has been finished in research repeatedly finally.
That is to say that the 1st invention of the present invention relates to, the preparation method of (1) a kind of Tai-Ace S 150 is characterized in that, makes the reaction of sulfuric acid and aluminium hydroxide in the presence of nitric acid; (2) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, reacts under the condition that also has aqueous hydrogen peroxide solution; (3) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, for all reaction systems, has nitric acid 1～3000ppm; (4) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, makes the sulfuric acid and the aluminium hydroxide reaction that contain nitric acid; (5) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, makes the sulfuric acid and the aluminium hydroxide reaction that contain nitric acid 10～5000ppm; (6) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, sulfuric acid is the vitriol oil of 50～90 weight %; (7) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, sulfuric acid is to be the used sulfuric acid of certain purpose; (8) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, aluminium hydroxide is to be the used aluminium hydroxide of certain purpose; (9) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, nitric acid is to be the used nitric acid of certain purpose; (10) a kind of Tai-Ace S 150 under the condition that nitric acid exists, obtains the reaction of sulfuric acid and aluminium hydroxide; (11) a kind of method that improves reaction yield during by sulfuric acid and preparation of aluminium hydroxide Tai-Ace S 150 is characterized in that, uses nitric acid; (12) nitric acid is in the purposes that is used for improving by the efficient of nitric acid and aluminium hydroxide prepared in reaction Tai-Ace S 150; (13) a kind of industrial composite is characterized in that, contains the Tai-Ace S 150 that sulfuric acid and aluminium hydroxide reaction are obtained; (14) above-mentioned (13) described industrial composite is a drainge treating agent; (15) a kind of drain treatment apparatus is equipped with industrial composite, and this industrial composite contains the Tai-Ace S 150 that sulfuric acid and aluminium hydroxide reaction are obtained.
In addition, the 2nd invention of the present invention relates to, and the preparation method of (1) a kind of Tai-Ace S 150 is characterized in that, makes sulfuric acid and aluminium hydroxide reaction under the condition that has the superoxide more than the 0.1 weight % for reaction system; (2) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that superoxide is a hydrogen peroxide; (3) preparation method of above-mentioned (2) described Tai-Ace S 150 is characterized in that hydrogen peroxide is an aqueous hydrogen peroxide solution; (4) preparation method of above-mentioned (3) described Tai-Ace S 150 is characterized in that, reacts under the condition that also has nitric acid; (5) preparation method of above-mentioned (3) described Tai-Ace S 150 is characterized in that, for reaction system, exists more than the aqueous hydrogen peroxide solution 0.1 weight %; (6) preparation method of above-mentioned (3) described Tai-Ace S 150 is characterized in that, makes to contain above sulfuric acid of aqueous hydrogen peroxide solution 0.2 weight % and aluminium hydroxide reaction; (7) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, sulfuric acid is the sulfuric acid of 50～90 weight %; (8) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, sulfuric acid is to be the used sulfuric acid of certain purpose; (9) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, aluminium hydroxide is to be the used aluminium hydroxide of certain purpose; (10) preparation method of above-mentioned (1) described Tai-Ace S 150 is characterized in that, aqueous hydrogen peroxide solution is to be the used aqueous hydrogen peroxide solution of certain purpose; (11) a kind of Tai-Ace S 150 under the condition that superoxide exists, obtains by making the reaction of sulfuric acid and aluminium hydroxide; (12) a kind of method that improves reaction yield during by sulfuric acid and preparation of aluminium hydroxide Tai-Ace S 150 is characterized in that, uses aqueous hydrogen peroxide solution; (13) superoxide is in the purposes that is used for improving by the efficient of sulfuric acid and aluminium hydroxide prepared in reaction Tai-Ace S 150; (14) a kind of industrial composite is characterized in that, contains the Tai-Ace S 150 that sulfuric acid and aluminium hydroxide reaction are obtained; (15) above-mentioned (10) described industrial composite is a drainge treating agent; (16) a kind of drain treatment apparatus is equipped with industrial composite, and this industrial composite contains the Tai-Ace S 150 that sulfuric acid and aluminium hydroxide reaction are obtained.
And the 3rd invention of the present invention relates to, and (1) a kind of industrial composite is characterized in that, contains nitric acid and Tai-Ace S 150; (2) above-mentioned (1) described industrial composite is characterized in that, contains 26.8 weight %Al with respect to being converted into
2(SO
4)
3The Tai-Ace S 150 weight of liquid Tai-Ace S 150, contain nitric acid 10～2000ppm; (3) above-mentioned (1) described industrial composite is characterized in that, nitric acid is to be the used nitric acid of certain purpose; (4) above-mentioned (1) described industrial composite is characterized in that, Tai-Ace S 150 is by being the thick Tai-Ace S 150 of the used sulfuric acid of certain purpose and nitric acid preparation; (5) above-mentioned (1) described industrial composite is a drainge treating agent; (6) above-mentioned (1) described industrial composite is paper cementing agent, the tanning agent of leather, greasy finings or industrial catalyst; (7) a kind of treatment process of draining is characterized in that, uses the composition that contains nitric acid and Tai-Ace S 150; (8) a kind of drain treatment apparatus is equipped with industrial composite, and this industrial composite contains nitric acid and Tai-Ace S 150.
Description of drawings
Fig. 1 represents comparison that the cohesion speed of the composition of the composition of the 3rd inventive embodiment 1～3 and comparative example 1,2 is carried out.
Fig. 2 represents the comparison that the turbidity to the composition of the composition of the 3rd inventive embodiment 1～3 and comparative example 1,2 carries out.
Fig. 3 represents comparison that the F ionic concn of the composition of the composition of the 3rd inventive embodiment 1～3 and comparative example 1,2 is carried out.
Embodiment
The sulfuric acid that uses in the 1st invention of the present invention, the 2nd invention and the 3rd invention is not particularly limited concentration, even the following concentration of about 90 weight % also can fully use, more than usually preferred about 50 weight %.In addition, in method in the past, vitriolic concentration is being standard more than the 90 weight %.In addition, as the vitriolic quality of using among the present invention, it can be the material of industrial or reagent grade, perhaps also can be the high purity product that in semi-conductor industry etc., use, also can be the material that uses as the washings of various parts or product, particularly in semi-conductive manufacturing process, peel off or material that washings uses as resist.In addition, also can be oleum or sulphuric anhydride or their degree liquid.In addition, from efficent use of resources, the viewpoint that reduces cost, wish to use and used sulfur waste acid once for certain purpose.
Above-mentionedly saidly, the used sulfuric acid of certain purpose contains vitriolic degree liquid, degree sulfuric acid etc. for comprising.
As the aluminium hydroxide that uses in the 1st invention of the present invention, the 2nd invention and the 3rd invention, it can be the material of the raw material use of industrial fire retardant, scagliola etc. as aluminium salt, porcelain, glass, refractory materials, catalyzer or support of the catalyst, resin, rubber, paper, also can be IC or optics with the high-purity hydrogen aluminum oxide that uses in frit, raffinal raw materials of compound, catalyzer, the medicine, can be the rejected material (used material) that contains aluminium hydroxide.In addition, from the viewpoint of cost aspect and efficent use of resources aspect, more preferably use industrial aluminium hydroxide or used aluminium hydroxide once as raw material for other purposes.
Above-mentionedly saidly comprise the rejected material that contains aluminium hydroxide etc. for the used aluminium hydroxide of certain purpose.
As the nitric acid that uses in the 1st invention of the present invention, the 2nd invention and the 3rd invention, can be that concentration and quality are any one material in reagent grade or the industrial level, also can be to contain to be certain purpose, the resist when for example organic synthesis, semiconductor production is peeled off, various washings etc. have been used the waste liquid of nitric acid once.In addition, also can be nitrosonitric acid or nitrosonitric acid degree liquid.From efficent use of resources, the viewpoint that reduces cost, wish to use and used waste nitric acid once for certain purpose.Perhaps, also can be the nitric acid composition that contains in the above-mentioned sulfuric acid.For example also can utilize as the spy and open flat 11-157812 or special open the scheme that proposes among the flat 11-319849 nitric acid that adds in order to decompose the aqueous hydrogen peroxide solution in the sulfation degree liquid, i.e. the nitric acid composition that contains in the sulfation degree liquid.
Above-mentionedly saidly comprise the degree liquid that contains nitric acid, degree nitric acid etc. for the used nitric acid of certain purpose.
The superoxide such as aqueous hydrogen peroxide solution that use in the 1st invention of the present invention, the 2nd invention and the 3rd invention, can be that concentration and quality are any one material in reagent grade or the industrial level, also can be to contain the waste liquid that has used aqueous hydrogen peroxide solution once for certain purpose.For example, can be the superoxide such as aqueous hydrogen peroxide solution that contain in the sulfuric acid waste that uses of the washings in semiconductor fabrication factory, peeled off etc. as resist.In addition, from efficent use of resources, the viewpoint that reduces cost, more wish the superoxide such as aqueous hydrogen peroxide solution that contain in this sulfur waste acid are used as raw material.
Above-mentionedly saidly comprise the aqueous hydrogen peroxide solution that contains in the degree liquid that contains superoxide such as aqueous hydrogen peroxide solution, the sulfur waste acid etc. for the used aqueous hydrogen peroxide solution of certain purpose.
In the 1st invention of the present invention, except that the raw material shown in above is sulfuric acid, aluminium hydroxide and nitric acid, also can make as required to have other additives in the reaction system, for example water carries out the preparation of Tai-Ace S 150.As reaction method, in making reaction system, exist the nitric acid, can carry out according to the preparation of known Tai-Ace S 150, can also can in sulfuric acid, add water aluminium hydroxide is made the material that slurries obtain with Powdered interpolation aluminium hydroxide in sulfuric acid.Perhaps, also can in the slurries of aluminium hydroxide and water, add sulfuric acid.In addition, nitric acid can add before reaction or in the reaction process arbitrarily, also can use with the state in the slurries that add sulfuric acid, water, aluminium hydroxide and water in advance to.Aforesaid spy opens in flat 11-157812 or the special black sulfuric acid of opening flat 11-319849 record has contained nitric acid.By using this sulfuric acid, also can make to have nitric acid in the reaction system as raw material.Reaction of the present invention is preferably undertaken by drip sulfuric acid in the mixture of aluminium hydroxide and nitric acid.
As the addition of nitric acid in this reaction system, for the gross weight of reaction system, be about 1～3000ppm, preferred about 10～1000ppm.If the addition of nitric acid is less than this scope, then be difficult to obtain to promote the effect of reacting, if it is be higher than this scope, then unfavorable economically.
In the 1st invention of the present invention, use the sulfuric acid contain nitric acid during as raw material, the concentration of nitric acid in the sulfuric acid is preferably about 10～5000ppm.This moment is same, if the addition of nitric acid is less than this scope, then is difficult to fully to obtain to promote the effect of reacting, and is if be higher than this scope, then unfavorable economically.
In addition, use the sulfuric acid that contains nitric acid, also can further in reaction system, add nitric acid.
In the 1st invention of the present invention, owing to can improve the vitriolic reactivity, therefore compare with method in the past by adding nitric acid, can use the sulfuric acid of lower concentration to promote reaction well at low temperature and short period of time internal efficiency.Its mechanism is still indeterminate, but predicts that following reaction is relevant with the reaction of Tai-Ace S 150.
H
2SO
4+HNO
3→NO
2++HSO
4 -
About the heating of reaction system owing to the effect that promotes reaction is arranged by above-mentioned nitric acid, and can utilize sulfuric acid and water hydration heat and with the reaction heat of aluminium, so there is no need to be provided with especially heating source.Therefore, temperature of reaction is fashionablely begun by room temperature adding, and by utilizing hydration heat and reaction heat, reaches about 60～110 ℃, slaking under this temperature then, thus can efficient prepare required Tai-Ace S 150 well.In addition, as required, also can for example utilize the pressure heating of steam etc.
Reaction times finished in about 1 minute～1 hour usually.About 1～20 minute of the dropping time (usually: about 5 minutes), about 1～20 minute of thermalization time (usually: about 5 minutes), but according to conditions such as temperature of reaction, also can be beyond this scope.
Aluminium hydroxide is with respect to preferably about 1.0～1.2 times of moles of vitriolic addition.
In addition, for the efficient that makes this reaction further improves, also can add aqueous hydrogen peroxide solution again.
In addition, reaction can be made by water and dilute the fraction that is adjusted into given concentration after being finished, and also can flow to and solidify bed, is cooled to completely solidified, with its pulverizing, packs then, makes product.
In above-mentioned the 1st invention, during by the prepared in reaction Tai-Ace S 150 of sulfuric acid and aluminium hydroxide, by there being nitric acid, the efficient of this reaction improves, and processing power improves, and speed of response improves, react at low temperatures, therefore become and to save energy,, therefore promoted saving resource, resources effective utilization owing to can utilize the sulfur waste acid of lower concentration.
In addition, the 1st the said industrial composite of invention of the present invention so long as contain the material of the Tai-Ace S 150 that the preparation method of the Tai-Ace S 150 by the 1st invention of the present invention prepares, can be any material.
In addition, the industrial composite of the 1st invention of the present invention can be according to known method, as uses such as drainge treating agent, paper cementing agent, the tanning agent of leather, greasy finings, various catalyzer.
And the industrial composite of the 1st invention can carry on devices such as draining processing in the past.
In the 2nd invention of the present invention, except that the raw material shown in above is superoxide such as sulfuric acid, aluminium hydroxide and aqueous hydrogen peroxide solution, as required, also can make to have other additives in the reaction system, water for example is to carry out the preparation of Tai-Ace S 150.As reaction method, in making reaction system, exist the superoxide such as aqueous hydrogen peroxide solution, can carry out according to the preparation of known Tai-Ace S 150, can also can in sulfuric acid, add aluminium hydroxide and water are made the material that slurries obtain with Powdered adding aluminium hydroxide in sulfuric acid.Perhaps, also can in the slurries of aluminium hydroxide and water, add sulfuric acid.In addition, superoxide such as aqueous hydrogen peroxide solution can add before reaction or in the reaction process arbitrarily, also can use with the state in the slurries that are added into sulfuric acid or water, aluminium hydroxide and water in advance.Reaction of the present invention is preferably undertaken by drip sulfuric acid in the mixture of superoxide such as aluminium hydroxide and aqueous hydrogen peroxide solution under agitation condition.
As the addition of superoxide such as aqueous hydrogen peroxide solution in this reaction system, be more than about 0.1 weight % with respect to the gross weight of reaction system (state before the water dilution).If the addition of superoxide such as aqueous hydrogen peroxide solution is less than this scope, then be difficult to obtain to promote the effect of reacting, in addition, if more than this scope, then unfavorable economically.
In the 2nd invention of the present invention, use the sulfuric acid contain superoxide such as aqueous hydrogen peroxide solution during as raw material, the concentration of superoxide such as the aqueous hydrogen peroxide solution in the preferably sulfuric acid is about more than the 0.2 weight %.This moment is same, if addition is less than this scope, then is difficult to fully to obtain to promote the effect of reacting, if more than this scope, then unfavorable economically.
In addition, also can contain in use on the vitriolic basis of superoxide such as aqueous hydrogen peroxide solution, in reaction system, further add superoxide such as aqueous hydrogen peroxide solution.
By making superoxide such as there being aqueous hydrogen peroxide solution in the reaction system, can in reaction, bring out superoxide such as aqueous hydrogen peroxide solution decomposition reaction (when superoxide is aqueous hydrogen peroxide solution, H
2O
2→ H
2O+1/2O
2T+98.4kJ), the fluid temperature that improves in the reaction system is made contributions.
Thus, can when realizing improving speed of response, also can finish reaction without heating source.Therefore, temperature of reaction is fashionablely begun by room temperature adding, reaction heat by utilizing vitriolic hydration heat, sulfuric acid and aluminium hydroxide and aqueous hydrogen peroxide solution decomposition heat, can reach about 70～110 ℃, then, under this temperature, be incubated/slaking, thereby can efficient prepare required Tai-Ace S 150 well.
In addition, in order further to improve the efficient of this reaction, also can in reaction system, add nitric acid, nitrosonitric acid or contain their waste liquid.
Reaction times finished in about 1 minute～1 hour usually.The dropping time finished in about 1～20 minute, and the situation that the curing time finished in about 1～20 minute is more.
Aluminium hydroxide is preferably about 1.0～1.2 times of moles with respect to the vitriolic addition.
In addition, reaction can be made by water and dilute the fraction that is adjusted into given concentration after being finished, and also can flow to and solidify bed, is cooled to completely solidified, with its pulverizing, packs then, makes product.
In the 2nd invention, during by the prepared in reaction Tai-Ace S 150 of sulfuric acid and aluminium hydroxide, by there being superoxide such as aqueous hydrogen peroxide solution, the efficient of this reaction improves, and processing power improves, and speed of response improves, react at low temperatures, therefore become and to save energy, can utilize the sulfur waste acid of lower concentration, promoted saving resource, resources effective utilization.
In addition, the 2nd the said industrial composite of invention of the present invention so long as contain the material of the Tai-Ace S 150 for preparing by preparation method of the present invention, can be any material.
In addition, the industrial composite of the 2nd invention of the present invention can be according to known method, as uses such as drainge treating agent, paper cementing agent, the tanning agent of leather, greasy finings, various catalyzer.
And the industrial composite of the 2nd invention can carry on devices such as draining processing in the past.
The Tai-Ace S 150 that uses in above-mentioned the 3rd invention can be to carry out and the fraction that obtains or in the Powdered thing any one according to the preparation of known Tai-Ace S 150, its quality can be an industrial level (industrial specification: JIS K 1423-1970, JIS K 1450-1977) or any one level in the reagent grade tap water specification:, perhaps, also can be the thick Tai-Ace S 150 made from used sulfur waste acid or useless aluminium hydroxide.
The industrial composite of the 3rd invention can easily be prepared by cooperating nitric acid and Tai-Ace S 150.Usually also contain water in the composition of the present invention.In addition, in the composition of the present invention, Tai-Ace S 150 exists as aqueous Tai-Ace S 150.Therefore, said aqueous Tai-Ace S 150 is made of water that exists in the composition and Tai-Ace S 150.
In the 3rd invention of the present invention,, the aggegation characteristic is improved, as its addition, with respect to being converted into aqueous Tai-Ace S 150 [Al by in Tai-Ace S 150, there being nitric acid
2O
3Content be 8 weight %, Al
2(SO
4)
3Content be 26.8 weight %] the weight of Tai-Ace S 150, wish to be about 10～2000ppm.If this scope of the concentration ratio of nitric acid is low, then can not expect the raising of aggegation effect, in addition,, then uneconomical if than this scope height.This nitric acid can directly add specified rate in aqueous Tai-Ace S 150, perhaps contain when preparation Tai-Ace S 150 or in its preparation raw material (sulfuric acid etc.) as mentioned above.
In addition, the 3rd inventive composition also can easily be prepared by the method that makes sulfuric acid and aluminium hydroxide reaction under the condition that exists at nitric acid.
As the addition of nitric acid in this reaction system, for the gross weight of reaction system, be about 1～3000ppm, preferred about 10～1000ppm.If the addition of nitric acid is less than this scope, then be difficult to obtain to promote the effect of reacting, if more than this scope, then unfavorable economically.
In addition, in the 3rd invention, when use contained the sulfuric acid of nitric acid as raw material, the concentration of nitric acid in the sulfuric acid was preferably about 10～5000ppm.This moment is same, if the addition of nitric acid is less than this scope, then is difficult to fully to obtain to promote the effect of reacting, if more than this scope, then unfavorable economically.
In addition, use the sulfuric acid that contains nitric acid, also can further in reaction system, add nitric acid.
In the 3rd invention of the present invention, owing to can improve the vitriolic reactivity, therefore compare with method in the past by adding nitric acid, can use the sulfuric acid of lower concentration to promote reaction well at low temperature and short period of time internal efficiency.Its mechanism is still indeterminate, but predicts that following reaction is relevant with the reaction of Tai-Ace S 150.
H
2SO
4+HNO
3→NO
2++HSO
4 -
About the heating of reaction system owing to the effect that promotes reaction is arranged by above-mentioned nitric acid, and can utilize sulfuric acid and water hydration heat and with the reaction heat of aluminium, so there is no need to be provided with especially heating source.Therefore, temperature of reaction is fashionablely begun by room temperature adding, and by utilizing hydration heat and reaction heat, reaches about 60～110 ℃, slaking under this temperature then, thus can efficient prepare required Tai-Ace S 150 well.In addition, as required, also can for example utilize the pressure heating of steam etc.
Reaction times finished in about 1 minute～1 hour usually.About 1～20 minute of the dropping time (usually: about 5 minutes), about 1～20 minute of the curing time (usually: about 5 minutes), but according to conditions such as temperature of reaction, also can be beyond this scope.
In the 3rd invention, aluminium hydroxide is with respect to preferably about 1.0～1.2 times of moles of vitriolic addition.
In addition, for the efficient that makes this reaction further improves, also can add aqueous hydrogen peroxide solution again.
In addition, reaction can be made by water and dilute the fraction that is adjusted into given concentration after being finished, and also can flow to and solidify bed, is cooled to completely solidified, then it is pulverized, and makes the composition of present method.
Obtain as mentioned above to comprise the industrial composite that nitric acid and Tai-Ace S 150 are feature, same with in the past Tai-Ace S 150 or PAC, can be used as drainge treating agent.
Think in addition and have nitric acid in the Tai-Ace S 150 by making, sulfate ion is easy to combine with nitrate ion, therefore sulfate ion dies down with aluminum ions the combination, the ionic strength of aluminium raises, the effect of the suspension particle in the absorption draining raises, and the industrial composite that contains Tai-Ace S 150 can be converted to the treatment agents such as drainge treating agent with agglutinating performance identical or above with PAC.
In addition, industrial composite of the present invention is same with in the past the composition that contains Tai-Ace S 150, except that drainge treating agent, can use in industrial circles such as the tanning agent of cementing agent, leather, greasy finings, various catalyzer at paper.
And industrial composite of the present invention can carry on devices such as draining processing in the past.
Embodiment
Further specify the 1st invention below by embodiment, but the present invention has more than and is limited to these.In addition, the quantitative analysis of the aluminum oxide in the Tai-Ace S 150 adopts JIS K1450-1996 method to carry out.
In the reactor that has agitator that covers the reactor outer wall with lagging material, add entry: 18g and Powdered aluminium hydroxide (reagent :): 9.8g with the pure medicine of light, stir, under agitation condition, in the material that room temperature obtains with 5 fens clockwise, drip the sulfuric acid (with reagent: and the pure medicine of light is adjusted to 80 weight %) of 80 weight %: 22.5g.Carry out slaking in 5 minutes after dripping end, in reaction solution, add entry: 28g then, dilute.The reaction solution that obtains is filtered with filter, separate unreacted aluminium hydroxide, make Tai-Ace S 150.
The 1st inventive embodiment 1
Before dripping sulfuric acid, in reactor, add 70 weight % nitric acid (industrial goods) 0.05g, react by aforesaid method.
The 1st inventive embodiment 2
The degree sulfuric acid from semiconductor factory (80 weight %) that use contains nitric acid 300ppm in addition, reacts by aforesaid method.
The 1st inventive embodiment 3
Use contains the degree sulfuric acid from semiconductor factory (80 weight %) of aqueous hydrogen peroxide solution 0.2 weight %, in addition, reacts by the method identical with embodiment 1.
The 1st inventive embodiment 4
When dilute with water, add the useless nitrosonitric acid as the resist stripper use of 0.05g in semiconductor factory, behind dilute with water, carry out 10 minutes slaking by waste heat, in addition, react by method same as described above.
The comparative example 1 of the 1st invention
Tai-Ace S 150 that will be by method for preparing as a comparative example 1.
The comparative example 2 of the 1st invention
Behind dilute with water, utilize waste heat to carry out 10 minutes slaking again, in addition.Adopt method same as described above to react.
To the comparative example 1,2 of the 1st inventive embodiment 1～4, the 1st invention, estimate the reacting liquid temperature, pH, the Al that drip after finishing
2O
3(weight %), evaluation result is concentrated and is shown in Table 1.
Table 1
As shown in Table 1, exist the 1st inventive embodiment 1～4 of nitric acid to compare with the comparative example 1,2 of the 1st invention, reaction efficiency improves, and the yield of aluminum oxide improves.In addition, even usage degree sulfuric acid, the yield of aluminum oxide improves too.If further add aqueous hydrogen peroxide solution, then the yield of aluminum oxide further improves.
Then, further specify the 2nd invention, but the present invention has more than and is limited to these by embodiment.In addition, the quantitative analysis of the aluminum oxide in the Tai-Ace S 150 adopts JIS K1450-1996 method to carry out.
In the reactor that has agitator that covers the reactor outer wall with lagging material, add entry: 18g and Powdered aluminium hydroxide (reagent :): 9.8g with the pure medicine of light, stir, under agitation condition, in the material that room temperature obtains with 5 fens clockwise, drip the sulfuric acid (with reagent: and the pure medicine of light is adjusted to 80 weight %) of 80 weight %: 22.5g.Carry out thermalization in 5 minutes after dripping end, in reaction solution, add entry: 28g then, dilute.The reaction solution that obtains is filtered with filter, separate unreacted aluminium hydroxide, make Tai-Ace S 150.
The 2nd inventive embodiment 1
Before dripping sulfuric acid, in reactor, add 30 weight % aqueous hydrogen peroxide solution (industrial goods) 1.0g, react by aforesaid method.
The 2nd inventive embodiment 2
The degree sulfuric acid from semiconductor factory (80 weight %) that use contains aqueous hydrogen peroxide solution 0.2% in addition, reacts by aforesaid method.
The 2nd inventive embodiment 3
Before dripping sulfuric acid, in reaction system, add the nitric acid (industrial goods) of 70 weight %: 0.05g, in addition, react by the method identical with embodiment 2.
The 2nd inventive embodiment 4
Add aqueous hydrogen peroxide solution and the water of 30 weight % in 98 weight % sulfuric acid, making sulfuric acid concentration is 80 weight %, and aqueous hydrogen peroxide solution concentration is 0.5 weight %, in addition, reacts by the method identical with embodiment 2.
The comparative example of the 2nd invention
Tai-Ace S 150 that will be by method for preparing as a comparative example.
The comparative example evaluation of the 2nd inventive embodiment 1～4, the 2nd invention is dripped temperature of reaction, pH, the Al of the reaction solution after finishing
2O
3(weight %), evaluation result is concentrated and is shown in Table 2.
Table 2
As shown in Table 2, exist the embodiment 1～4 of aqueous hydrogen peroxide solution to compare with comparative example, reaction efficiency improves, and the yield of aluminum oxide improves.In addition, even use sulfur waste acid, the yield of aluminum oxide improves too.If further add nitric acid, then the yield of aluminum oxide further improves.
Then, further specify the 3rd invention, but the present invention has more than and is limited to these by embodiment.In addition, the quantitative analysis of the aluminum oxide in the Tai-Ace S 150 adopts JIS K1450-1996 method to carry out.
The 3rd inventive embodiment 1
Add the material that industrial nitric acid (70 weight %) 500ppm forms at following comparative example 1 described tap water in Tai-Ace S 150.
The 3rd inventive embodiment 2
In the reactor that has agitator that covers the reactor outer wall with lagging material, add entry: 18g and Powdered aluminium hydroxide (reagent): 9.8g and 70 weight % nitric acid (industrial goods): 0.05g, stir, under agitation condition, in the material that room temperature obtains with 5 fens clockwise, drip the sulfuric acid of 80 weight %: 22.5g.Carry out slaking in 5 minutes after dripping end, in reaction solution, add entry: 28g then, dilute.The reaction solution that obtains is filtered with filter, separate unreacted aluminium hydroxide, to substance-measuring pH and the Al that obtains
2O
3(weight %).The pH of this liquid is 3.33, Al
2O
3(weight %) is 8.10.
The 3rd inventive embodiment 3
Do not add nitric acid itself, and use the sulfur waste acid from semiconductor factory (80 weight %) contain nitric acid 300ppm, react by the method identical with embodiment 1.The pH of the reaction solution that finally obtains is 3.12, Al
2O
3(weight %) is 8.14.
The comparative example 1 of the 3rd invention
Tap water Tai-Ace S 150 (Al
2O
3: 8 weight %), pH is 3.10, Al
2O
3(weight %) is 8.10.
The comparative example 2 of the 3rd invention
(the polymerize aluminum chloride: industrial goods with PAC is handled in draining; Aluminum oxide 10 weight %).
Use above-mentioned 5 kinds of samples, by semiconductor factory's draining comparative evaluation aggegation effect.In addition, in the former water of this draining, contain F ion 30ppm (in this draining, also containing sulfuric acid, nitric acid, hydrochloric acid etc. in addition), to wherein adding white lime to pH=8.7, the suspension liquid that use obtains, to adding the situation of each sample, and the situation of then adding polymer coagulant (polyacrylamide agglutinant), compare investigation with the project of aggegation speed, turbidity, F ionic concn.In addition, for aggegation speed, use sediment tube to measure by time to set a distance by visual inspection.The turbidity of draining uses the portable turbidometer PC-06 of capital of a country electronic industry (strain) to measure, and the F ionic concn uses the DKK IL0-30 of company to measure.
Comparative example 1,2 to the 3rd inventive embodiment 1～3, the 3rd invention is estimated aggegation speed, turbidity, F ionic concn, the results are shown in Fig. 1～3.
By the result of Fig. 1 as can be known, exist the embodiment 1～3 of nitric acid to compare, show good aggegation speed with comparative example 1,2.In addition, the addition of sample is many more, then shows better aggegation speed more.
By the result of Fig. 2 as can be known, exist the embodiment 1～3 of nitric acid to compare, show that turbidity reduces with comparative example 1,2.In addition, if add other polymer coagulants again, show that then turbidity further reduces.
By the result of Fig. 3 as can be known, exist the embodiment 1～3 of nitric acid to compare, show that the F ionic concn reduces with comparative example 1,2.In addition, if add other polymer coagulants again, show that then the F ionic concn further reduces.
The invention effect
According to the present invention, about 50～90 % by weight that will contain from the Waste Sulfuric Acid of semiconductor factory The sulfuric acid of concentration can efficient prepare aluminum sulfate well as raw material.
Compare with method in the past, by there being the peroxidating such as nitric acid or aqueous hydrogen peroxide solution Thing can promote reaction, and reaction system reaches maximum temperature at short notice, finishes reaction, Disposal ability improves, and the energy that reducing heating needs causes saving energy, reduces unreacted reactant and leads Causing quality improves. That is to say, have nitric acid in the reaction system by making, can improve sulfuric acid The preparation efficiency of aluminium.
Aluminum sulfate by preparation method's preparation of the present invention can be at sewage, plant chimney stalk, Shang Shui Deng drainge treating agent, paper cementing agent, the tanning agent of leather or the fining agent of grease, various catalysis Use as industrial composite in the agent etc.
The aluminum sulfate compositions display cohesion performance better than PAC that contains nitric acid of the present invention.
In addition because can usage degree sulfuric acid, degree nitric acid, therefore can efficent use of resources.
Claims (5)
1, a kind of waste water conditioner, it contains Tai-Ace S 150, and the nitric acid of 10～2000ppm, and wherein the described content of nitric acid is described Tai-Ace S 150 to be converted into contain 26.8 weight %Al
2(SO
4)
3Liquid Tai-Ace S 150 and calculate based on the weight of this liquid Tai-Ace S 150.
2, the described waste water conditioner of claim 1, wherein said nitric acid are to be the used nitric acid of certain purpose.
3, the described waste water conditioner of claim 1, wherein said Tai-Ace S 150 are by being the thick Tai-Ace S 150 of the used sulfuric acid of certain purpose and nitric acid preparation.
4, a kind of method of wastewater treatment, it comprises any described waste water conditioner in the use claim 1,2 and 3.
5, a kind of wastewater treatment equipment, it uses any described waste water conditioner in the claim 1,2 and 3.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001356385A JP4343467B2 (en) | 2001-11-21 | 2001-11-21 | Method for producing aluminum sulfate |
| JP356386/2001 | 2001-11-21 | ||
| JP356385/2001 | 2001-11-21 | ||
| JP356387/2001 | 2001-11-21 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021505810A Division CN1296281C (en) | 2001-11-21 | 2002-11-21 | Aluminium sulfate, its preparation method and use thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1951836A CN1951836A (en) | 2007-04-25 |
| CN100537441C true CN100537441C (en) | 2009-09-09 |
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ID=19167913
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2006101630988A Expired - Fee Related CN100537441C (en) | 2001-11-21 | 2002-11-21 | Aluminum sulfate, production method for aluminum sulfate and its uses |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4343467B2 (en) |
| CN (1) | CN100537441C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4165313B2 (en) * | 2003-06-25 | 2008-10-15 | ソニー株式会社 | Inorganic flocculant and wastewater treatment method |
| JP4457027B2 (en) * | 2005-02-22 | 2010-04-28 | 新日本製鐵株式会社 | Disposal water treatment method |
| KR102044937B1 (en) * | 2018-09-17 | 2019-11-14 | 미주엔비켐 주식회사 | Preparing method of inorganic coagulant for waste water treatment using low concentration sulfuric acid solution and purification method of waste water using the inorganic coagulant prepared by the same |
-
2001
- 2001-11-21 JP JP2001356385A patent/JP4343467B2/en not_active Expired - Fee Related
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2002
- 2002-11-21 CN CNB2006101630988A patent/CN100537441C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1951836A (en) | 2007-04-25 |
| JP2003160334A (en) | 2003-06-03 |
| JP4343467B2 (en) | 2009-10-14 |
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