CN110028258A - A kind of method that iron Sulphur ressource is utilized respectively in titanium gypsum - Google Patents
A kind of method that iron Sulphur ressource is utilized respectively in titanium gypsum Download PDFInfo
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- CN110028258A CN110028258A CN201910405735.5A CN201910405735A CN110028258A CN 110028258 A CN110028258 A CN 110028258A CN 201910405735 A CN201910405735 A CN 201910405735A CN 110028258 A CN110028258 A CN 110028258A
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- gypsum
- titanium gypsum
- titanium
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- utilized respectively
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- 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
- C04B11/007—After-treatment of the dehydration products, e.g. aging, stabilisation
-
- 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
- C04B11/02—Methods and apparatus for dehydrating gypsum
- C04B11/028—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained
- C04B11/032—Devices therefor characterised by the type of calcining devices used therefor or by the type of hemihydrate obtained for the wet process, e.g. dehydrating in solution or under saturated vapour conditions, i.e. to obtain alpha-hemihydrate
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- 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
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P3/00—Preparation of elements or inorganic compounds except carbon dioxide
Abstract
This patent discloses the methods that iron Sulphur ressource in a kind of titanium gypsum is utilized respectively, and water, gypsum modifying agent, water modifying agent is added after mixing evenly in titanium gypsum, are pumped into physical separation device, isolated white titanium gypsum and red titanium gypsum；PH stabilizer is added in the white titanium gypsum of physical separation device discharge, occurs to turn brilliant reaction in pipeline reactor to obtain semi-hydrated gypsum, by after semi-hydrated gypsum physics shaping, adjustable solidification agent is added, drying breaks up to obtain high strength gypsum dry powder；The red titanium gypsum of physical separation device discharge, is added carbon source and microorganism is aged to obtain iron sulfide.Compared with prior art scheme, the characteristics of this method production cost is low, high production efficiency, good product quality.
Description
Technical field
The present invention relates to the resource utilization fields of industrial residue, and in particular to titanium gypsum high-qualityization utilizes.
Background technique
China was titanium resource big country, the world, and mineral type is mainly ilmenite, according to US Geological Survey in 2015
(USGS) data announced, 200,000,000 tons of China's titanium Iron Ore Reserve, Zhan Quanqiu reserves 28%, the ranking whole world first.The primary ferrotianium in the whole nation
Mine shares at 45, is mainly distributed on Panxi, Sichuan and Chengde.According to association, China Non-Ferrous Metals Industry Tai Gao hafnium branch with
The joint of Pan Gangtai industry group counts, and the whole nation produces 3,800,000 tons of ilmenite concentrate altogether within 2014, wherein 2,540,000 tons of Panxi Diqu.
Ilmenite is titanium dioxide mainly for the production of titanium dioxide, the main component of titanium dioxide, and chemical property is stablized, tool
Have well color fastness and excellent covering power, it is considered to be best white pigment in the world at present.2015, China's titanium
White powder production, more than 2,300,000 tons.
There are mainly two types of methods for industrial production titanium dioxide: chloridising and sulfuric acid process.Titanium gypsum is using Production By Sulfuric Acid Process
When titanium dioxide, to administer acid waste water, it is added in lime stone and calcium oxide and acid waste water and the waste residue that generates, it is main
Ingredient is dihydrate gypsum and iron hydroxide, and to guarantee iron precipitating thoroughly, micro- excess is added in calcium oxide, and titanium gypsum shows alkalescent.Titanium
The discharge of gypsum does not only take up a large amount of soils, and pollutes environment.Due to the flushing by rainwater, piling up the titanium gypsum on field can be sent out
It is raw to be lost, meanwhile, titanium gypsum passes through rainwash and immersion, and soluble detrimental substance is soluble in water, in the environment through water
Flowing and circulation, can serious polluted surface water and underground water；On the other hand, titanium gypsum accumulation is after solarization wind, small part
It can be drifted in atmosphere with powdered, and be deposited to the foreign object surface being likely to be exposed, not only pollute environment but also [Lee that poses a health risk
State is loyal, Zhao Shuai, Yu Yang titanium gypsum the field of building materials application study [J] brick and tile, 2008, (3): 58-60].
Screw(-type) feeder is exactly to be mounted with flight on center shaft, and axis and flight rotate in a fixed shell,
Mechanical device with transferring raw material function.When changing the spiral shell diameter or screw pitch of spiral, the conveying capacity of batcher will be sent out
It is raw to change, raw material is accumulated in batcher by the variation of batcher conveying capacity, thus play the role of raw material sealing, this
Be exactly material envelope [Yi Xiaolu, Zhang Xiaodong, Guo Dongyan wait Investigation on screw feedstock seal equipment in CFB [J] renewable energy,
2004, (5): 41-43].
Industrial gypsum is dihydrate gypsum, occurs to turn brilliant reaction for (110-180 DEG C) generally under autoclaved condition, obtains half water stone
Cream.To obtain the semi-hydrated gypsum of morphology controllable, it is commonly incorporated into crystal modifier, obtains high strength gypsum；The present invention is adjusted molten using buffer
Liquid pH realizes semi-hydrated gypsum Morphological control, has the characteristics of control is simple, and pattern is easy to control.It is used in size control kettle
Mechanical stirring and the method for Ceramic Balls mechanical shaping control gypsum crystal partial size are continuously distributed.
Since titanium gypsum contains iron hydroxide, moisture content is high, is not easy to dry, and added value is low.This patent realizes that titanium gypsum is high
Added value utilizes, and solves the problems, such as that titanium gypsum recycles.
Summary of the invention
In order to solve the problems existing in the prior art, the present invention provides the sides that iron Sulphur ressource in a kind of titanium gypsum is utilized respectively
Method, compared with prior art scheme, this method can save production cost, reduce energy consumption, improve efficiency, and have significant economic effect
Benefit and social benefit.
A kind of method that iron Sulphur ressource is utilized respectively in titanium gypsum, comprising the following steps:
Water, gypsum modifying agent, water modifying agent is added after mixing evenly in titanium gypsum, is pumped into physical separation device, it is isolated white
Color titanium gypsum and red titanium gypsum；PH stabilizer is added in the white titanium gypsum of physical separation device discharge, in pipeline reactor
Occur to turn brilliant reaction to obtain semi-hydrated gypsum, by after semi-hydrated gypsum physics shaping, adjustable solidification agent is added, drying breaks up to obtain high strength gypsum
Dry powder；The red titanium gypsum of physical separation device discharge, is added carbon source and microorganism is aged to obtain iron sulfide.
The additional amount of the water is the 100-200% of titanium gypsum quality.
The gypsum modifying agent is rosin soap, alkyl benzene calcium sulfonate, calcium lignosulfonate, polycarboxylic acids calcium, oxidized paraffin wax
One of soap and its derivative, additional amount are the 0.01-0.5% of titanium gypsum quality.
The water modifying agent is one of eucalyptus oil, methyl isobutyl carbinol, cresotinic acid, and additional amount is ardealite matter
The 0.01-0.5% of amount.
The pH stabilizer is calcium glycolate, calcium phthalate, calcium disodium chelate, calcium gluconate
One of, additional amount is the 0.01-0.5% of gypsum quality.
The pipeline reactor is designed according to the principle of screw conveyor.
The physics is shaped as stirring ball-milling, is stirred using anchor formula, and added with Ceramic Balls.
The adjustable solidification agent is one of secondary amide albumen, gelatine, modified mycelia, polycarboxylic acids, and additional amount is gypsum matter
The 0.01-0.5% of amount.
Compared with the existing technology, the invention has the following advantages that
Gypsum modifying agent can be adsorbed on titanium gypsum surface, improve the surface nature of titanium gypsum, avoid iron hydroxide in gypsum table
Face absorption, while making gypsum that there is certain hydrophobicity, and increase the dispersibility of gypsum.
Water modifying agent can change the viscosity of water, and the stability of bubble can be improved in physical separation device, is conducive to gypsum
With bubble floating.
Physical separation device is designed according to the principle of gravity treatment, flotation, and main component is attached most importance to flotation column.It is added in titanium gypsum
The slurry that water, gypsum modifying agent, water modifying agent obtain after mixing evenly is entered from the feed inlet of physical separation device by pump and is floated again
Select column；Air enters weight flotation column through dispersion plate by air intake.Air enter weight flotation column mode be pulse into
Enter, weight flotation column is made to have the function of jigging sorting.Air forms bubble in weight flotation column, gypsum be adsorbed on bubble surface to
Upper movement excludes from top discharge mouth, obtains white titanium gypsum.Iron hydroxide and a small amount of gypsum since gravity moves downward,
It is discharged from lower part discharge port.This equipment utilization physical method has high-efficient, without secondary pollution feature.In addition, white titanium stone
The water generated when cream, red titanium gypsum filters pressing, it is Ke Xunhuanliyong.
During gypsum occurs to turn brilliant, dihydrate gypsum dissolving-recrystallization is changed into semi-hydrated gypsum, and the pH of solution will affect
The structure and pattern of semi-hydrated gypsum crystal grain can be 1.5-6.5 with the pH value of stablizing solution by pH stabilizer, be conducive to obtain
The crystal grain of axis.PH value of solution is too low to be easy to get anhydrous gypsum；The too high dissolution that will affect dihydrate gypsum of pH influences to turn brilliant reaction.
In addition, if the pH Tai Gaokejia of titanium gypsum a small amount of Waste Sulfuric Acid, reduces its pH value.
Pipeline reactor is designed according to the principle of screw conveyor, and gypsum is entered by pump from pipeline reactor entrance,
It under helical blade rotation drives, travels forward, before the discharge port of pipeline reactor, the screw pitch for changing helical blade forms material envelope
The pressure in reactor is kept to stablize, 110-180 DEG C of reaction temperature.Material seal apparatus is set according to the principle that screw feeder material seals
Meter has structure simple, the good feature of sealing effect, it is ensured that the pressure not pressure release in still kettle, with continuous discharge
Feature.
Semi-hydrated gypsum is grown in free environment is easy to get the close crystal grain of particle size, and physics shaping can be brilliant by part
Grain is broken, and rodlike crystal grain the shaft-like crystal grain such as can also be broken into, in obtained high strength gypsum powder the crystal grain of semi-hydrated gypsum from
50nm-20 μm of continuously distributed equi-axed crystal.The continuously distributed crystal grain of partial size advantageously reduces gypsum after semi-hydrated gypsum aquation
Gap in body, to be conducive to improve the intensity of gypsum.In addition, little crystal grain is nanoscale elder generation aquation when semi-hydrated gypsum aquation
At dihydrate gypsum nucleus, has the function of crystal seed, being conducive to semi-hydrated gypsum crystallization is fibrous dihydrate gypsum, two obtained water stones
Cream crystal grain is tiny, intersects, to improve gypsum intensity.
Semi-hydrated gypsum is turning brilliant temperature hereinafter, being easy to react generation dihydrate gypsum with water or with the water in air, thus shadow
Ring the quality and intensity of product.Adjustable solidification agent is added in high strength gypsum, semi-hydrated gypsum can be hindered to hydrolyze, under guaranteeing its intensity not
Drop.Since the setting time of gypsum is shorter, adjustable solidification agent, which is added, can extend the gypsum sets time, be conducive to construct；This patent is high-strength
The setting time of gypsum is 30-120min, has preferable retarding effect.Secondary amide albumen is the egg containing secondary amide group
White, modified mycelia is to produce the waste that penicillin or erythromycin generate, and polycarboxylic acids is containing there are two carboxyls；These retarder have
There is preferable deferred action, and declines gypsum intensity.
Dry break up realizes that the equipment is hammer mill resistant to high temperature or centrifugal crusher and heat by dry beater
Wind furnace composition, has the characteristics that rate of drying is fast.Material high-speed is thrown to shock plate using centrifugal force by centrifugal crusher, makes material
It is broken.It is half water building gypsum that two water titanium gypsums can also be dehydrated by dry beater, is used as cementitious material.
Carbon source is one of branch or stalk, the waste (animal wastes, fur, internal organ etc.) of farm's discharge, is led to
Cross what compost obtained, additional amount is the 10-30% of titanium gypsum quality.Microorganism is sulfate reducing bacteria, is common microbiological, often
Additional amount is 10 in kilogram titanium gypsum6It is a.Sulfate reducing bacteria under anaerobic, by the gypsum reduction in red titanium gypsum at
Hydrogen sulfide, hydrogen sulfide reacts to obtain iron sulfide with the iron hydroxide in red gypsum, while absorption water and knot in iron hydroxide
Brilliant water emits, and is conducive to the drying of product.It is 30-300 days that carbon source and the time of microorganism ageing, which is added, in red titanium gypsum.
Iron sulfide heat resolve obtains sulfur dioxide gas and iron oxide, and sulfur dioxide gas is used to prepare sulfuric acid, oxidation
Iron can be used as iron ore for making steel, and realize iron sulfur cycle.
Specific embodiment
Below in conjunction with specific embodiment, invention is further described in detail.
(1) water, gypsum modifying agent, water modifying agent is added after mixing evenly in titanium gypsum, is pumped into physical separation device, separate
Obtain white titanium gypsum and red titanium gypsum.Composition of raw materials is shown in Table 1.
Table 1
In the present embodiment 1- embodiment 16, the whiteness of white gypsum is all larger than 60%.
PH stabilizer is added in the white titanium gypsum of physical separation device discharge, turns crystalline substance in pipeline reactor and reacts
To semi-hydrated gypsum, by after semi-hydrated gypsum physics shaping, adjustable solidification agent is added, drying breaks up to obtain high strength gypsum dry powder；Physical separation
The red titanium gypsum of device discharge, is added carbon source and microorganism is aged to obtain iron sulfide.The additional amount of pH stabilizer, adjustable solidification agent, is shown in
Table 2.
Table 2
From embodiment 1- embodiment 16, it can be concluded that, obtained high strength gypsum does compression strength and is all larger than 75MPa；Red titanium gypsum
In gypsum conversion ratio be 100%.
The embodiment of the present invention can be implemented and can reach goal of the invention.The present invention is not limited to these Examples.
Claims (8)
1. a kind of method that iron Sulphur ressource is utilized respectively in titanium gypsum, which is characterized in that successively include the following steps:
Water, gypsum modifying agent, water modifying agent is added after mixing evenly in titanium gypsum, is pumped into physical separation device, it is isolated white
Color titanium gypsum and red titanium gypsum；PH stabilizer is added in the white titanium gypsum of physical separation device discharge, in pipeline reactor
Occur to turn brilliant reaction to obtain semi-hydrated gypsum, by after semi-hydrated gypsum physics shaping, adjustable solidification agent is added, drying breaks up to obtain high strength gypsum
Dry powder；The red titanium gypsum of physical separation device discharge, is added carbon source and microorganism is aged to obtain iron sulfide.
2. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that the water
Additional amount be titanium gypsum quality 100-200%.
3. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that its feature
Be, the gypsum modifying agent be rosin soap, alkyl benzene calcium sulfonate, calcium lignosulfonate, polycarboxylic acids calcium, oxidized paraffin wax soap and
One of its derivative, additional amount are the 0.01-0.5% of titanium gypsum quality.
4. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that its feature
It is, the water modifying agent is one of eucalyptus oil, methyl isobutyl carbinol, cresotinic acid, and additional amount is phosphogypsum quality
0.01-0.5%.
5. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that its feature
It is, the pH stabilizer is calcium glycolate, in calcium phthalate, calcium disodium chelate, calcium gluconate
One kind, additional amount are the 0.01-0.5% of gypsum quality.
6. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that described
Pipeline reactor is designed according to the principle of screw conveyor.
7. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that described
Physics is shaped as stirring ball-milling, is stirred using anchor formula, and added with Ceramic Balls.
8. the method that iron Sulphur ressource is utilized respectively in a kind of titanium gypsum according to claim 1, which is characterized in that described
Adjustable solidification agent is one of secondary amide albumen, gelatine, modified mycelia, polycarboxylic acids, and additional amount is the 0.01-0.5% of gypsum quality.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110372245A (en) * | 2019-08-05 | 2019-10-25 | 西南科技大学 | A kind of method that industry by-product gypsum cascade utilization prepares sulphur calcium ferrite |
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| CN109734341A (en) * | 2019-03-13 | 2019-05-10 | 西南科技大学 | A kind of method that ardealite physical chemistry brightened and prepared cementitious material |
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| CN105765091A (en) * | 2013-11-22 | 2016-07-13 | 芬兰国家技术研究中心股份公司 | Method for recovering rare earth metals from waste sulphates |
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Cited By (2)
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| CN110372245A (en) * | 2019-08-05 | 2019-10-25 | 西南科技大学 | A kind of method that industry by-product gypsum cascade utilization prepares sulphur calcium ferrite |
| CN110372245B (en) * | 2019-08-05 | 2021-09-17 | 西南科技大学 | Method for preparing calcium pyrite by gradient utilization of industrial byproduct gypsum |
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