CN106477616A - The manufacture method of Gypsum Fibrosum and the manufacture method of cement composition - Google Patents
The manufacture method of Gypsum Fibrosum and the manufacture method of cement composition Download PDFInfo
- Publication number
- CN106477616A CN106477616A CN201610427972.8A CN201610427972A CN106477616A CN 106477616 A CN106477616 A CN 106477616A CN 201610427972 A CN201610427972 A CN 201610427972A CN 106477616 A CN106477616 A CN 106477616A
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- China
- Prior art keywords
- gypsum fibrosum
- sulfuric acid
- waste sulfuric
- manufacture method
- calcium source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B11/00—Calcium sulfate cements
- C04B11/26—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke
- C04B11/262—Calcium sulfate cements strating from chemical gypsum; starting from phosphogypsum or from waste, e.g. purification products of smoke waste gypsum other than phosphogypsum
- C04B11/264—Gypsum from the desulfurisation of flue gases
Abstract
The present invention provides a kind of manufacture method of Gypsum Fibrosum and the manufacture method of cement composition.The manufacture method of the Gypsum Fibrosum of the present invention includes：Add calcium source in the Waste Sulfuric Acid containing fluorine, make the step (A) that Gypsum Fibrosum separates out when maintaining into the pH of Waste Sulfuric Acid below 2.0；The Gypsum Fibrosum being separated out in step (A) is separated from Waste Sulfuric Acid the step (B) removing；Add calcium source to separating in step (B) in the Waste Sulfuric Acid eliminate Gypsum Fibrosum, makes the step (C) that Gypsum Fibrosum separates out when the pH of Waste Sulfuric Acid is maintained into 2.5～4.0；The Gypsum Fibrosum being separated out in step (C) is separated from Waste Sulfuric Acid the step (D) removing；Add calcium source to separating in step (D) in the Waste Sulfuric Acid eliminate Gypsum Fibrosum, makes the step (E) that Gypsum Fibrosum separates out when the pH of Waste Sulfuric Acid is maintained into 6.0～8.0；And the Gypsum Fibrosum being separated out in step (E) is separated from Waste Sulfuric Acid the step (F) removing.The method of the present invention is more more effective than former method.
Description
Technical field
The present invention relates to the manufacture method of a kind of manufacture method of Gypsum Fibrosum and cement composition.
Background technology
Using calcium compounds, process is neutralized to produced Waste Sulfuric Acid in various industrial steps, and manufactures work
Method for the Gypsum Fibrosum of its by-product is widely known by the people.But, with regard to the Waste Sulfuric Acid containing many fluorine, if being only neutralized process,
Then the Oil repellent in Gypsum Fibrosum also uprises, therefore as Gypsum Fibrosum using being limited to.Therefore, in the past in order to from the sulfur waste containing fluorine
Obtain the low Gypsum Fibrosum of the content of fluorine in acid, simultaneously pH is maintained into 2.5 ± 0.3 scope, so that calcium compounds is entered with sulphuric acid
Row reaction, thus manufactures Gypsum Fibrosum (referring for example to patent documentation 1) from Waste Sulfuric Acid.
[prior art literature]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 9-67118 publication
Content of the invention
[inventing problem to be solved]
But, manufacturing the method for Gypsum Fibrosum from Waste Sulfuric Acid described in patent documentation 1, carrying out to manufacture Gypsum Fibrosum
Also the SO that many becomes the raw material of Gypsum Fibrosum is remained in Waste Sulfuric Acid after process4 2-, and expect the further effectively sharp of Waste Sulfuric Acid
With.Therefore, the manufacturer of the Gypsum Fibrosum of Waste Sulfuric Acid it is an object of the invention to provide one kind is compared with the past, can more effectively be utilized
Method, and the manufacture of the cement composition of cement composition is manufactured using the Gypsum Fibrosum manufactured by the manufacture method by described Gypsum Fibrosum
Method.
[technological means of solve problem]
Present inventor etc. carries out making great efforts the result of research, finds to separate out and carry out separating from the low Gypsum Fibrosum of the content making fluorine to go
Make the high Gypsum Fibrosum precipitation of the content of fluorine in Waste Sulfuric Acid after removing, and reduce the content of the fluorine in Waste Sulfuric Acid, and make Gypsum Fibrosum from reduction
Separate out further in the described Waste Sulfuric Acid of the content of fluorine, thus can more effectively utilize the SO in Waste Sulfuric Acid4 2-As Gypsum Fibrosum,
Thus completing the present invention.That is, the present invention is as described below.
[1] a kind of manufacture method of Gypsum Fibrosum is it is characterised in that include：Add calcium source in the Waste Sulfuric Acid containing fluorine, simultaneously
The pH of Waste Sulfuric Acid is maintained into less than 2.0 steps (A) simultaneously making Gypsum Fibrosum precipitation；By the Gypsum Fibrosum being separated out in step (A) from useless
The step (B) removing is separated in sulphuric acid；Add calcium source to separating in step (B) in the Waste Sulfuric Acid eliminate Gypsum Fibrosum, simultaneously will
The pH of Waste Sulfuric Acid maintains into the step (C) that 2.5～4.0 one sides make Gypsum Fibrosum separate out；By the Gypsum Fibrosum being separated out in step (C) from sulfur waste
The step (D) removing is separated in acid；Add calcium source to separating in the Waste Sulfuric Acid eliminate Gypsum Fibrosum in step (D), simultaneously will give up
The pH of sulphuric acid maintains into the step (E) that 6.0～8.0 one sides make Gypsum Fibrosum separate out；And by the Gypsum Fibrosum being separated out in step (E) from useless
The step (F) removing is separated in sulphuric acid.
[2] Gypsum Fibrosum according to described in described [1] manufacture method it is characterised in that：Step (A) is to giving up containing fluorine
Add calcium source in sulphuric acid, so that Gypsum Fibrosum is separated out.
[3] Gypsum Fibrosum according to described in described [1] or [2] manufacture method it is characterised in that：Step (C) is to separation
Eliminate interpolation calcium source in the Waste Sulfuric Acid of Gypsum Fibrosum, so that Gypsum Fibrosum is separated out.
[4] according to any one of described [1] to [3] record Gypsum Fibrosum manufacture method it is characterised in that：In step (A)
The calcium source being used is Calcium Carbonate.
[5] according to any one of described [1] to [4] record Gypsum Fibrosum manufacture method it is characterised in that：In step (C)
The calcium source being used is calcium hydroxide.
[6] according to any one of described [1] to [5] record Gypsum Fibrosum manufacture method it is characterised in that：In step (E)
The calcium source being used is calcium hydroxide.
[7] a kind of manufacture method of cement composition it is characterised in that：Remember using according to any one of described [1] to [6]
The Gypsum Fibrosum of the Gypsum Fibrosum of separated removal and separated removal in step (F) in step (B) in the manufacture method of Gypsum Fibrosum carrying
At least one Gypsum Fibrosum is manufacturing cement composition.
(The effect of invention)
According to the present invention, it is possible to provide one kind, compared with the past, can more effectively utilize the manufacture method of the Gypsum Fibrosum of Waste Sulfuric Acid,
And the manufacturer of the cement composition of cement composition is manufactured using the Gypsum Fibrosum manufactured by the manufacture method by described Gypsum Fibrosum
Method.
Specific embodiment
[manufacture method of Gypsum Fibrosum]
Hereinafter, the manufacture method of the Gypsum Fibrosum of the present invention is illustrated.The manufacture method of the Gypsum Fibrosum of the present invention includes：Xiang Han
There is interpolation calcium source in the Waste Sulfuric Acid of fluorine, make the step (A) that Gypsum Fibrosum separates out when maintaining into the pH of Waste Sulfuric Acid below 2.0；
The Gypsum Fibrosum being separated out in step (A) is separated from Waste Sulfuric Acid the step (B) removing；Eliminate stone to separating in step (B)
Add calcium source in the Waste Sulfuric Acid of cream, make the step (C) that Gypsum Fibrosum separates out when the pH of Waste Sulfuric Acid is maintained into 2.5～4.0；Will
The Gypsum Fibrosum being separated out in step (C) separates the step (D) removing from Waste Sulfuric Acid；Eliminate Gypsum Fibrosum to separating in step (D)
Waste Sulfuric Acid in add calcium source, make when the pH of Waste Sulfuric Acid is maintained into 6.0～8.0 Gypsum Fibrosum separate out step (E)；And
The Gypsum Fibrosum being separated out in step (E) is separated from Waste Sulfuric Acid the step (F) removing.
Step (A)
In step (A), add calcium source in the Waste Sulfuric Acid containing fluorine, simultaneously the pH of Waste Sulfuric Acid is maintained into less than 2.0
Gypsum Fibrosum is simultaneously made to separate out.
(Waste Sulfuric Acid)
Step (A) as long as used in Waste Sulfuric Acid contain fluorine person, then be not particularly limited.Waste Sulfuric Acid example containing fluorine
Reclaim vulcanised ore concentrate in this way as the SO in the aerofluxuss of the nonferrous metal refining furnace of raw material2Manufactured Waste Sulfuric Acid.Described row
Gas contains fluorine, and therefore Waste Sulfuric Acid also contains fluorine.
(calcium source)
Calcium source used in step (A) be the compound containing calcium and using these compounds as main constituent various materials
Material, as long as Gypsum Fibrosum with epigenesist, is then not particularly limited.Calcium source for example can be enumerated：Calcium oxide, calcium hydroxide, Calcium Carbonate and phosphorus
Sour calcium etc..Alternatively, it is also possible to big for the content of the calcium such as shell or unprocessed concrete mud (concrete sludge) is given up
Gurry is used as calcium source.These calcium sources can be used alone one kind or be used in combination of two or more.Among these calcium sources, preferably
Calcium source is Calcium Carbonate.Furthermore, the calcium source of pulverulence can be added to Waste Sulfuric Acid it is also possible to add the calcium source of slurry form
To Waste Sulfuric Acid.
(addition of calcium source)
The addition of calcium source is to maintain into less than 2.0 with the pH of the Waste Sulfuric Acid by being added with calcium source, preferably maintain into 1.5 with
Under mode be controlled.
(Gypsum Fibrosum)
The Gypsum Fibrosum being separated out in step (A) is dihydrate gypsum.Fluorine in Waste Sulfuric Acid will not separate out, and remains in Waste Sulfuric Acid
In, the content of the fluorine in the Gypsum Fibrosum therefore being separated out in step (A) is little.
(pH of Waste Sulfuric Acid)
In step (A), by Waste Sulfuric Acid add calcium source to make Gypsum Fibrosum separate out when Waste Sulfuric Acid pH maintain into 2.0 with
Under, preferably maintain into less than 1.5.If the pH of Waste Sulfuric Acid is more than 2.0, the precipitation quantitative change of the calcium fluoride together separating out with Gypsum Fibrosum
Greatly, the fluorine in Gypsum Fibrosum is big containing quantitative change.As long as in addition, Gypsum Fibrosum separates out, then when adding calcium source in Waste Sulfuric Acid to make Gypsum Fibrosum separate out
The lower limit of the pH of Waste Sulfuric Acid be not particularly limited.For example, the lower limit of the pH of Waste Sulfuric Acid is 1.0.
(water)
In step (A), in order to adjust viscosity of the Waste Sulfuric Acid being added with calcium source etc. it is also possible to add in Waste Sulfuric Acid
Water.The water that can be used for the manufacture method of the Gypsum Fibrosum of the present invention for example can be enumerated：Ion exchange water, pure water, distilled water and tap water
Deng.These water can be used alone one kind or be used in combination of two or more.Furthermore, can also in the step beyond step (A)
Add water in Waste Sulfuric Acid.
Step (B)
In step (B), the Gypsum Fibrosum being separated out is separated from Waste Sulfuric Acid remove in step (A).
(separate and remove)
Can be removed it is also possible to pass through to the sulfur waste containing Gypsum Fibrosum by making gypsum deposition separate Gypsum Fibrosum from Waste Sulfuric Acid
Acid carries out filtration and Gypsum Fibrosum separates from Waste Sulfuric Acid removal.Alternatively, it is also possible to using using liquid cyclone, decanter, from
Gypsum Fibrosum is separated from Waste Sulfuric Acid and removes by the separation method of the equipment for separating liquid from solid such as centrifugal separator, pressure filter.These separate and go
Except method can individually be implemented it is also possible to implement two or more combinations.
Step (C)
In step (C), add calcium source to separating in the Waste Sulfuric Acid eliminate Gypsum Fibrosum in step (B), simultaneously by sulfur waste
The pH of acid maintains into 2.5～4.0 one sides makes Gypsum Fibrosum separate out.
(Waste Sulfuric Acid)
Waste Sulfuric Acid used in step (C) is to separate the Waste Sulfuric Acid eliminating Gypsum Fibrosum in step (B).
(calcium source)
Calcium source used in step (C) be the compound containing calcium and using these compounds as main constituent various materials
Material, as long as Gypsum Fibrosum with epigenesist, is then not particularly limited.Calcium source for example can be enumerated：Calcium oxide, calcium hydroxide, Calcium Carbonate and phosphorus
Sour calcium etc..Alternatively, it is also possible to garbage big for the content of the calcium such as shell or unprocessed concrete mud is used as calcium source.These
Calcium source can be used alone one kind or be used in combination of two or more.Among these calcium sources, preferred calcium source is calcium hydroxide.Again
Person, can add to Waste Sulfuric Acid the calcium source of pulverulence it is also possible to add the calcium source of slurry form to Waste Sulfuric Acid.
(addition of calcium source)
The addition of calcium source is to maintain into 2.5～4.0 with the pH of the Waste Sulfuric Acid by being added with calcium source, preferably maintains into 2.5
～3.0 mode is controlled.
(Gypsum Fibrosum)
The Gypsum Fibrosum being separated out in step (C) is dihydrate gypsum.Fluorine in Waste Sulfuric Acid mostly as calcium fluoride and stone
Cream together separates out, the fluorine in the Gypsum Fibrosum therefore being separated out in step (C) big containing quantitative change, and the fluorine in Waste Sulfuric Acid containing quantitative change
Little.
The Gypsum Fibrosum being separated out in step (C) can also be discarded.But, exist containing fluorine as required in cement composition
Micro constitutent person.Accordingly it is also possible to the Gypsum Fibrosum being separated out in step (C) is used as the raw material of this kind of cement composition.
(pH of Waste Sulfuric Acid)
In step (C), the pH of the Waste Sulfuric Acid adding in Waste Sulfuric Acid when calcium source to make Gypsum Fibrosum separate out is maintained into 2.5～
4.0, preferably maintain into 2.5～3.0.If the pH of Waste Sulfuric Acid is less than 2.5, there is the most of fluorine conduct that cannot make in Waste Sulfuric Acid
Calcium fluoride and situation about together separating out with Gypsum Fibrosum.In the case, will be useless after the Separation of gypsum being separated out in step (C) removal
Fluorine in sulphuric acid big containing quantitative change.If in addition, the pH of Waste Sulfuric Acid is more than 4.0, the quantitative change of the Gypsum Fibrosum that can reclaim in step (E)
Few.
Step (D)
In step (D), the Gypsum Fibrosum being separated out is separated from Waste Sulfuric Acid remove in step (C).
(separate and remove)
The explanation that the explanation that separation in step (D) removes is removed with the separation in step (B) is identical, therefore omits step
(D) explanation that the separation in removes.Furthermore, the method that separation in step (D) removes can remove with separating in step (B)
Method identical it is also possible to different.In addition, becoming faster it is also possible to add polymer coagulant in order that separating.
Step (E)
In step (E), add calcium source to separating in the Waste Sulfuric Acid eliminate Gypsum Fibrosum in step (D), simultaneously by sulfur waste
The pH of acid maintains into 6.0～8.0 one sides makes Gypsum Fibrosum separate out.Thus, can make in described step (A) not as Gypsum Fibrosum precipitation
SO4 2-Separate out further from Waste Sulfuric Acid, and can more effectively utilize Waste Sulfuric Acid.
(Waste Sulfuric Acid)
Waste Sulfuric Acid used in step (E) is to separate the Waste Sulfuric Acid eliminating Gypsum Fibrosum in step (D).
(calcium source)
Calcium source used in step (E) be the compound containing calcium and using these compounds as main constituent various materials
Material, as long as Gypsum Fibrosum with epigenesist, is then not particularly limited.Calcium source for example can be enumerated：Calcium oxide, calcium hydroxide, Calcium Carbonate and phosphorus
Sour calcium etc..Alternatively, it is also possible to garbage big for the content of the calcium such as shell or unprocessed concrete mud is used as calcium source.These
Calcium source can be used alone one kind or be used in combination of two or more.Among these calcium sources, preferred calcium source is calcium hydroxide.Again
Person, can add to Waste Sulfuric Acid the calcium source of pulverulence it is also possible to add the calcium source of slurry form to Waste Sulfuric Acid.
(addition of calcium source)
The addition of calcium source is to maintain into 6.0～8.0 with the pH of the Waste Sulfuric Acid by being added with calcium source, preferably maintains into 6.5
～7.5 mode is controlled.
(Gypsum Fibrosum)
The Gypsum Fibrosum being separated out in step (E) is dihydrate gypsum.As described above, in step (C), fluorine in Waste Sulfuric Acid big
Part is together separated out with Gypsum Fibrosum as calcium fluoride.Therefore, the content of the fluorine in the Gypsum Fibrosum being separated out in step (E) diminishes.
(pH of Waste Sulfuric Acid)
In step (E), the pH of the Waste Sulfuric Acid adding in Waste Sulfuric Acid during calcium source is maintained into 6.0～8.0, preferably maintains
Become 6.5～7.5.If the pH being added with the Waste Sulfuric Acid of calcium source is less than 6.0, there is the SO remaining in Waste Sulfuric Acid4 2-Containing quantitative change
Big situation, if the pH being added with the Waste Sulfuric Acid of calcium source is more than 8.0, exist not with the containing of sulfur waste acid reaction and the calcium source that remains
The big situation of quantitative change.
Step (F)
In step (F), the Gypsum Fibrosum being separated out is separated from Waste Sulfuric Acid remove in step (E).
(separate and remove)
The explanation that the explanation that separation in step (F) removes is removed with the separation in step (B) is identical, therefore omits step
(F) explanation that the separation in removes.Furthermore, the method that separation in step (F) removes can remove with separating in step (B)
Method identical it is also possible to different.In addition, becoming faster it is also possible to add polymer coagulant in order that separating.
The Waste Sulfuric Acid eliminating Gypsum Fibrosum in the middle separation of step (F) can also be processed directly as waste liquid.In addition, also may be used
To be re-used for manufacturing Gypsum Fibrosum from Waste Sulfuric Acid by separating the Waste Sulfuric Acid eliminating Gypsum Fibrosum in step (F).For example, it is also possible to will be
Separate in step (F) and eliminate the Waste Sulfuric Acid of Gypsum Fibrosum and be used as medium during the slurry making calcium source or in order to adjust interpolation calcium source
The medium of the viscosity of Waste Sulfuric Acid afterwards.
[manufacture method of cement composition]
The manufacture method of the cement composition of the present invention is using institute in the step (B) in the manufacture method of Gypsum Fibrosum of the present invention
At least one Gypsum Fibrosum separating the Gypsum Fibrosum of separated removal in the Gypsum Fibrosum removing and step (F) is manufacturing cement composition.Example
As it is also possible to in cement clinker (cement clinker) add the present invention Gypsum Fibrosum manufacture method step (B) in institute
Separate the Gypsum Fibrosum removing to manufacture cement composition with a small amount of blending constituent.Alternatively, it is also possible to by the system of the Gypsum Fibrosum of the present invention
The Gypsum Fibrosum making separated removal in the step (B) of method is used as in the cement clinker manufactured by one of molten slag raw material, adds this
In the step (B) of the manufacture method of bright Gypsum Fibrosum, the Gypsum Fibrosum of separated removal or other Gypsum Fibrosum to manufacture water with a small amount of blending constituent
Mud compositionss.And then, it is possible to use the Gypsum Fibrosum of separated removal in the step (F) in the manufacture method of the Gypsum Fibrosum of the present invention comes
Replace in step (B) Gypsum Fibrosum of separated removal or go separated in the step (F) in the manufacture method of the Gypsum Fibrosum of the present invention
The Gypsum Fibrosum removing is used along with the Gypsum Fibrosum of separated removal in step (B).Thus, can effectively utilizes by the Gypsum Fibrosum of the present invention
Gypsum Fibrosum manufactured by manufacture method is as the raw material of cement composition.
[embodiment]
Then, the present invention is illustrated in greater detail by embodiment, but the present invention is not subject to any restriction of these embodiments.
[measure and evaluate]
Measure and evaluate the Gypsum Fibrosum manufactured by the manufacture method of Gypsum Fibrosum by embodiment and adjoint described system as following
Make produced Waste Sulfuric Acid.
(1) pH of Waste Sulfuric Acid
Using pH meter, (hole field makes institute's (share) and manufactures, trade name：PH meter D-51), (hole field makes institute (stock to pH electrode
Part) manufacture, trade name：Sleeve ToupH electrode 9681-10D), measure the pH of the Waste Sulfuric Acid being added with calcium source.
(2) identification of precipitate
Using X-ray around injection device, the mirror of the precipitate separating out from Waste Sulfuric Acid after carrying out adding calcium source in Waste Sulfuric Acid
Fixed.
(3) content of the fluorine in precipitate
Using combustion-type ion chromatography apparatus, measure the precipitate separating out from Waste Sulfuric Acid after adding calcium source in Waste Sulfuric Acid
In Oil repellent.
(4) content of the fluorine in Waste Sulfuric Acid
Using Flow Injection Analysis device, measure Oil repellent Waste Sulfuric Acid being filtered in obtained Waste Sulfuric Acid.
(5) SO in Waste Sulfuric Acid4 2-Content
Using ion chromatography apparatus, measure SO Waste Sulfuric Acid being filtered in obtained Waste Sulfuric Acid4 2-Content.
[manufacture method of the Gypsum Fibrosum of embodiment]
(embodiment 1)
(the 1st stage)
Add Calcium Carbonate to make the pH of Waste Sulfuric Acid become 2.0 in Waste Sulfuric Acid.Then, Waste Sulfuric Acid is filtered and obtained
The precipitate of Waste Sulfuric Acid and filtered Waste Sulfuric Acid.
(the 2nd stage)
Add calcium hydroxide to make the pH of Waste Sulfuric Acid become 3.0 in the Waste Sulfuric Acid obtain in the 1st stage filtration.So
Afterwards, Waste Sulfuric Acid is filtered and obtained the precipitate of Waste Sulfuric Acid and filtered Waste Sulfuric Acid.
(the 3rd stage)
Add calcium hydroxide to make the pH of Waste Sulfuric Acid become 6.5 in the Waste Sulfuric Acid obtain in the 2nd stage filtration.So
Afterwards, Waste Sulfuric Acid is filtered and obtained the precipitate of Waste Sulfuric Acid and filtered Waste Sulfuric Acid.
[measurement result and evaluation result]
The evaluation result of the precipitate obtained in the manufacture method of the Gypsum Fibrosum of embodiment 1 and Waste Sulfuric Acid is shown in Table 1.
[table 1]
The manufacture method of the Gypsum Fibrosum of table 1 embodiment 1
Evaluation result according to embodiment 1 it is known that the low Gypsum Fibrosum of content that fluorine not only can be obtained in the 1st stage, the 3rd
The low Gypsum Fibrosum of the content of fluorine can also be obtained in stage.Thus it is known that with only implement the situation phase using Waste Sulfuric Acid for the 1st stage
The manufacture method of the Gypsum Fibrosum of embodiment 1 can more effectively utilize the SO in Waste Sulfuric Acid to ratio4 2-.
Claims (4)
1. a kind of manufacture method of Gypsum Fibrosum is it is characterised in that include：
Step (A), adds calcium source in the Waste Sulfuric Acid containing fluorine, makes stone when maintaining into the pH of Waste Sulfuric Acid below 2.0
Cream separates out；
Step (B), the described Gypsum Fibrosum being separated out is separated from described Waste Sulfuric Acid remove in described step (A)；
Step (c), adds calcium source to separating in described step (B) in the described Waste Sulfuric Acid eliminate described Gypsum Fibrosum, simultaneously will
The pH of described Waste Sulfuric Acid maintains into 2.5～4.0 one sides makes Gypsum Fibrosum separate out；
Step (D), the described Gypsum Fibrosum being separated out is separated from described Waste Sulfuric Acid remove in described step (C)；
Step (E), adds calcium source to separating in described step (D) in the described Waste Sulfuric Acid eliminate described Gypsum Fibrosum, simultaneously will
The pH of described Waste Sulfuric Acid maintains into 6.0～8.0 one sides makes Gypsum Fibrosum separate out；And
Step (F), the described Gypsum Fibrosum being separated out is separated from described Waste Sulfuric Acid remove in described step (E).
2. Gypsum Fibrosum according to claim 1 manufacture method it is characterised in that：Described step (A) is to contain fluorine to described
Waste Sulfuric Acid in add described calcium source, make when maintaining into the pH of described Waste Sulfuric Acid below 1.5 Gypsum Fibrosum separate out.
3. Gypsum Fibrosum according to claim 1 and 2 manufacture method it is characterised in that：Described step (c) is to remove to separation
Add described calcium source in the described Waste Sulfuric Acid of described Gypsum Fibrosum, make when the pH of described Waste Sulfuric Acid is maintained into 2.5～3.0
Gypsum Fibrosum separates out.
4. a kind of manufacture method of cement composition it is characterised in that：Using according to any one of claim 1 to 3
The stone of separated removal in the Gypsum Fibrosum of separated removal and described step (F) in described step (B) in the manufacture method of Gypsum Fibrosum
At least one Gypsum Fibrosum in cream is manufacturing cement composition.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015165596A JP6409713B2 (en) | 2015-08-25 | 2015-08-25 | Method for producing gypsum and method for producing cement composition |
| JP2015-165596 | 2015-08-25 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106477616A true CN106477616A (en) | 2017-03-08 |
| CN106477616B CN106477616B (en) | 2020-05-19 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610427972.8A Active CN106477616B (en) | 2015-08-25 | 2016-06-16 | Method for producing gypsum and method for producing cement composition |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6409713B2 (en) |
| KR (1) | KR102474446B1 (en) |
| CN (1) | CN106477616B (en) |
| TW (1) | TWI694970B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6975406B2 (en) * | 2018-02-16 | 2021-12-01 | 三菱マテリアル株式会社 | A method for controlling the amount of aluminum dissolved and a method for producing gypsum based on the method. |
| KR102038332B1 (en) * | 2018-03-26 | 2019-10-30 | 신유근 | Manufacturing method of Gypsum for Cement using Phospho-gypsum |
| KR102156734B1 (en) * | 2019-02-15 | 2020-09-17 | 주식회사 티아이 | Methods To manufacture alkaline waste neutralizer of solids containing large amounts of active calcium oxide by mixing raw lime with bauxite residues and neutralizing sulfuric acid as industrial materials such as cement condensation retardant |
| KR102285409B1 (en) * | 2021-01-21 | 2021-08-03 | 이충수 | A gypsum manufacturing system using waste sulfuric acid and gypsum manufactured by the system |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0967118A (en) * | 1995-08-28 | 1997-03-11 | Sumitomo Metal Mining Co Ltd | Production of gypsum from sulfuric acid waste liquid |
| CN101580265A (en) * | 2009-04-08 | 2009-11-18 | 王嘉兴 | Method for preparing gypsum and dry ice from limestone and waste sulfuric acid |
| CN102030354A (en) * | 2010-10-18 | 2011-04-27 | 中蓝连海设计研究院 | Treatment method of waste sulfuric acid |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4374810A (en) * | 1978-06-01 | 1983-02-22 | Agrico Chemical Company | Recovery of fluorine from pond water of wet process phosphoric acid plants and recycling of defluorinated water |
| JPS5934644B2 (en) * | 1980-06-13 | 1984-08-23 | 日本鉱業株式会社 | Fluorine removal method from waste sulfuric acid |
| JPH0910548A (en) * | 1995-06-29 | 1997-01-14 | Mitsubishi Heavy Ind Ltd | Treatment of drain containing fluorine |
| JPH11228134A (en) * | 1998-02-16 | 1999-08-24 | Sumitomo Metal Mining Co Ltd | Production of gypsum dihydrate |
| JP4156390B2 (en) * | 2003-01-31 | 2008-09-24 | 株式会社トクヤマ | Cement production method |
| WO2008050737A1 (en) * | 2006-10-23 | 2008-05-02 | Sumitomo Osaka Cement Co., Ltd. | Method of treating asbestos-containing waste material |
| JP5138737B2 (en) * | 2010-06-29 | 2013-02-06 | パンパシフィック・カッパー株式会社 | Method for producing waste acid gypsum |
| WO2014174647A1 (en) * | 2013-04-25 | 2014-10-30 | 三菱重工業株式会社 | Water treatment method and water treatment system |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0967118A (en) * | 1995-08-28 | 1997-03-11 | Sumitomo Metal Mining Co Ltd | Production of gypsum from sulfuric acid waste liquid |
| CN101580265A (en) * | 2009-04-08 | 2009-11-18 | 王嘉兴 | Method for preparing gypsum and dry ice from limestone and waste sulfuric acid |
| CN102030354A (en) * | 2010-10-18 | 2011-04-27 | 中蓝连海设计研究院 | Treatment method of waste sulfuric acid |
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| CN106477616B (en) | 2020-05-19 |
| KR102474446B1 (en) | 2022-12-06 |
| KR20170024523A (en) | 2017-03-07 |
| TWI694970B (en) | 2020-06-01 |
| JP6409713B2 (en) | 2018-10-24 |
| JP2017043503A (en) | 2017-03-02 |
| TW201708114A (en) | 2017-03-01 |
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