CN109292809A - The application of the method for purification, gypsum and gypsum of titanium gypsum - Google Patents
The application of the method for purification, gypsum and gypsum of titanium gypsum Download PDFInfo
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- CN109292809A CN109292809A CN201811166947.4A CN201811166947A CN109292809A CN 109292809 A CN109292809 A CN 109292809A CN 201811166947 A CN201811166947 A CN 201811166947A CN 109292809 A CN109292809 A CN 109292809A
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- Prior art keywords
- gypsum
- flotation
- purification
- titanium
- titanium gypsum
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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
- C01F11/468—Purification of calcium sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/002—Inorganic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/016—Macromolecular compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/005—Dispersants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/007—Modifying reagents for adjusting pH or conductivity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/06—Depressants
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention provides the applications of a kind of method of purification of titanium gypsum, gypsum and gypsum, are related to the technical field of industrial chemicals processing.The method of purification of titanium gypsum provided by the invention, including sizing mixing, flotation and separation, wherein, in flotation step, used flotation agent includes capturing agent, optional foaming agent, optional dispersing agent, optional activator, optional inhibitor and optional pH regulator.This method of purification simple process reduces the cost for purification of titanium gypsum, is rich in iron in the by-product obtained after purification, can be used for sintered ironmaking, realize the efficient utilization of titanium gypsum.Gypsum provided by the invention, the purity is high of the dihydrate gypsum contained can substitute the natural gypsum as construction material, to alleviate the problem of titanium gypsum excessively cannot be rehoused and utilize and cause the wasting of resources and environmental pollution completely.
Description
Technical field
The present invention relates to industrial chemicals manufacture fields, more particularly, to a kind of method of purification of titanium gypsum, gypsum and gypsum
Application.
Background technique
Titanium dioxide is one of the white pigment that performance is best now, is widely used in coating, plastics, papermaking, chemical fibre, makeup
The industries such as product, production method is based on sulfuric acid process.However by-product titanium will be generated using sulfuric acid process 1 ton of titanium dioxide of every production
5~6 tons of gypsum, China generates about 8,000,000 tons of titanium gypsum every year.If these titanium gypsums cannot be disposed and be utilized well, not only
It will cause the wasting of resources, and can cause seriously to pollute to ecological environment.
The main component of titanium gypsum is dihydrate gypsum, and impurity is mainly iron, magnesium, aluminium and titanium.The content of iron is most in impurity
Height, mainly with Fe2O3Form exist.Since the content of gypsum in titanium gypsum is low, color is partially red or partially yellow, using effect and
Application range is severely impacted.Currently, titanium gypsum is only used for construction material such as cement retarder, mixing cementing material, road floor
Material etc., using extremely limiting to.
To realize making full use of for titanium gypsum, need to purify titanium gypsum, removal influences the main miscellaneous of its color
Matter Fe2O3.Currently, the method for purification of titanium gypsum mainly has recrystallization method, the precipitation method and organic extraction.Using three of the above side
Though method can effectively realize the purification to titanium gypsum, have the defects that certain.Recrystallization method technique is cumbersome, and energy consumption is high；
Precipitation method filtration difficulty, it is inconvenient；Organic extraction is at high cost.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first purpose of this invention is to provide a kind of method of purification of titanium gypsum, and simple process, production cost is low, can
To overcome the above problem or at least be partially solved the above problem.
Second object of the present invention is to provide a kind of gypsum, which purifies to obtain by titanium gypsum, to alleviate titanium
The problem of gypsum excessively cannot be rehoused and utilize and cause the wasting of resources and environmental pollution.
Third object of the present invention is to provide a kind of application of gypsum in construction material, and the gypsum purified can
To replace the natural gypsum completely.
In order to solve the above-mentioned technical problem, the following technical scheme is adopted:
According to the first aspect of the invention, the present invention provides a kind of methods of purification of titanium gypsum, including size mixing, flotation and
Separation；
Wherein, in the flotation step, used flotation agent includes capturing agent, optional foaming agent, optional dispersion
Agent, optional activator, optional inhibitor and optional pH regulator.
As further technical solution, in the step of sizing mixing, by titanium gypsum and water to be processed according to mass ratio be 1:3
~20 are uniformly mixed；
Preferably, in the step of sizing mixing, titanium gypsum to be processed is mixed according to mass ratio for 1:5~10 with water
It is even；
Preferably, the water further includes the water that separating step obtains.
As further technical solution, in the flotation step, flotation agent is added into the ore pulp sized mixing, mixing is equal
It is even, it carries out flotation and obtains concentrate foam and tailing ore pulp.
As further technical solution, the capturing agent includes neopelex, lauryl sodium sulfate, oleic acid
At least one of sodium and sodium salicylate；
Preferably, the mass ratio of the additional amount of the capturing agent and titanium gypsum be 0.3~2:1000, preferably 0.5~
1.2:1000；
Preferably, the foaming agent includes at least one of terpinol, camphorated oil, pinke needle oil and butyl ether oil；
Preferably, the mass ratio of the additional amount of the foaming agent and titanium gypsum be 0.3~2:1000, preferably 0.5~
1.2:1000；
Preferably, the dispersing agent includes in ethyl alcohol, waterglass, calcium stearate, calgon, cellulose and glycerol
It is at least one；
Preferably, the mass ratio of the additional amount of the dispersing agent and ore pulp is 1~10:1000；
Preferably, the activator includes at least one of sulfuric acid, sulfurous acid, oxalic acid and sodium carbonate；
Preferably, the mass ratio of the additional amount of the activator and titanium gypsum be 0.3~2:1000, preferably 0.5~
1.2:1000；
Preferably, the inhibitor includes at least one of vulcanized sodium, lime, dextrin and starch；
Preferably, the mass ratio of the additional amount of the inhibitor and titanium gypsum be 0.3~2:1000, preferably 0.5~
1.2:1000；
Preferably, the pH regulator includes at least one of sulfuric acid, hydrochloric acid, sodium hydroxide and calcium hydroxide；
Preferably, the pH of ore pulp is adjusted to 6~8 using pH regulator.
As further technical solution, the flotation is a flotation or multiple flotation.
It is described to be uniformly mixed to be uniformly mixed by churned mechanically mode as further technical solution.
As further technical solution, in the separating step, the concentrate foam and tailing ore pulp that respectively obtain flotation
It is separated by solid-liquid separation, obtains gypsum and rich iron charge；
Preferably, described be separated by solid-liquid separation includes at least one of sedimentation, filtering and centrifugation；
It preferably, further include drying steps after the solid-liquid separation step.
As further technical solution, the isolated water returns to step cycle use of sizing mixing.
According to the second aspect of the invention, the present invention provides a kind of gypsum that the method for purification using titanium gypsum obtains.
According to the third aspect of the invention we, the application the present invention provides a kind of gypsum in construction material.
Compared with prior art, the present invention include it is following the utility model has the advantages that
The method of purification of titanium gypsum provided by the invention, by the way that successively titanium gypsum is sized mixing, flotation and lock out operation
Purification gypsum is obtained, simple process reduces the cost for purification of titanium gypsum, is rich in iron in the by-product obtained after purification, can use
In sintered ironmaking, the efficient utilization of titanium gypsum is realized.Gypsum provided by the invention, the purity is high of the dihydrate gypsum contained, can
The substitution natural gypsum completely excessively cannot be rehoused and be utilized and cause the wasting of resources to alleviate titanium gypsum as construction material
And the problem of environmental pollution.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, is also possible to obtain other drawings based on these drawings.
Fig. 1 is the method for purification flow chart of titanium gypsum provided in an embodiment of the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiments and examples, but this field skill
Art personnel will be understood that following embodiments and embodiment are merely to illustrate the present invention, and are not construed as limiting model of the invention
It encloses.Based on the embodiments of the present invention, obtained by those of ordinary skill in the art without making creative efforts
Every other embodiment, shall fall within the protection scope of the present invention.The person that is not specified actual conditions, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
In a first aspect, the present invention provides a kind of methods of purification of titanium gypsum, including size mixing, flotation and separation, wherein floating
Select in step, used flotation agent include capturing agent, optional foaming agent, optional dispersing agent, optional activator, optionally
Inhibitor and optional pH regulator.
Titanium gypsum is the Main By product of sulfuric acid legal system titanium dioxide, and main component is dihydrate gypsum, and impurity is mainly
Iron, magnesium, aluminium and titanium.The content highest of iron in impurity, mainly with Fe2O3Form exist.Due to the content of gypsum in titanium gypsum
Low, color is partially red or partially yellow, and using effect and application range are severely impacted.Currently, titanium gypsum is only used for construction material
Such as cement retarder, mixing cementing material, road layer material.It realizes making full use of for titanium gypsum, needs to carry out titanium gypsum
Purification, removal influence the major impurity Fe of its color2O3。
Floatation is suitable for by floatingly selecting mineral from ore pulp using the physics of mineral surfaces and the difference of chemical property
The thin dip dyeing ore of particle is sorted, is had a wide range of applications in mining processing industry.Flotation agent is common reagent in floatation process,
It can be used for adjusting the chemical property of flotation material and flotation medium, to expand the floatability difference of flotation storeroom, improve flotation
Efficiency.Flotation agent includes capturing agent, foaming agent, dispersing agent, activator, inhibitor and pH regulator.
Capturing agent by the polar group that can have an effect with mineral particle surface and hydrophobic effect non-polar group group
At.Due to the surface of most of mineral grains be it is hydrophilic, carry out flotation when need to be improved its floatability.Capturing agent is added to mine
After in slurry, it can be adsorbed on the surface of mineral grain, polar group forms hydrophobic outwardly towards mineral particle surface, non-polar group
Film makes mineral grain have floatability, realizes the flotation of mineral.
Foaming agent is the surface active molecules with hydrophilic radical and hydrophobic grouping, orientable to be adsorbed on gas-liquid interface, is dropped
The surface tension of low solution makes the air being filled be easy to disperse into bubble, and generates stable foam.Foaming agent has with capturing agent
Synergy is adsorbed in mineral particle surface jointly, and mineral is promoted to float.
Dispersing agent is mainly used for that thin ore particle is prevented to assemble, and biggish ore particle is dispersed into fine grained, and is allowed in monomer
Dispersity.
Activator can enhance mineral with the binding ability of capturing agent, and indissoluble mineral is made to be activated and be floated.
Inhibitor can improve mineral hydrophily or mineral is prevented to act on capturing agent, be suppressed its floatability.
PH regulator is by adjusting mash acid alkalinity, control mineral surfaces characteristic, ore pulp chemical composition and various medicaments
Action condition, improve flotation effect.
It should be noted that above-mentioned " optionally " refer to above-mentioned foaming agent, dispersing agent, activator, inhibitor and pH tune
Whole dose can add, and can not also add.When only using capturing agent, the floatability of gypsum can be improved, realize the floating of gypsum
Choosing；Further, after adding foaming agent, dispersing agent, activator, inhibitor and pH regulator, capturing agent and stone can be reinforced
The combination of cream improves the floatability of gypsum, improves flotation effect.It, can according to the actual situation or process requirements in practical application
It is added.
The present invention extracts the gypsum in titanium gypsum, and Fe using floatation2O3Equal impurity stay in ore pulp, to realize to titanium stone
The purification of cream.According to the present invention, titanium gypsum is uniformly mixed with water according to certain volume ratio first, is tuned into ore pulp, then to
Flotation agent is added in ore pulp, is uniformly mixed, and is carried out flotation and is obtained concentrate foam and tailing ore pulp, the concentrate for finally obtaining flotation
Foam and tailing ore pulp are separated by solid-liquid separation, and purification gypsum and rich iron charge are obtained.
Present invention process is simple, reduces the cost for purification of titanium gypsum, is rich in iron in the by-product obtained after purification, can use
In sintered ironmaking, the efficient utilization of titanium gypsum is realized.
As further technical solution, in step of sizing mixing, by titanium gypsum and water to be processed according to mass ratio be 1:3~20
It is uniformly mixed.
In the present invention, titanium gypsum and the typical but non-limiting volume ratio of water are as follows: 1:3,1:5,1:7,1:9,1:11,1:
13,1:15,1:17,1:19 or 1:20.
In the present invention, titanium gypsum and water are subjected to the ore pulp for being mixed to get suitable flotation, the ratio of titanium gypsum and water
The effect of flotation is influenced, when the ratio of titanium gypsum and water is smaller, the concentration of ore pulp is diluter, needs to add more flotation agent
The flotation effect of rationality can be reached, production capacity is low；When the large percentage of titanium gypsum and water, ore pulp is excessively sticky, is unfavorable for
Mineral grain dispersion, influences separating effect.
Preferably, in step of sizing mixing, titanium gypsum to be processed is uniformly mixed with water according to mass ratio for 1:5~10.
By the further adjustment and optimization to titanium gypsum and water volume ratio, so that the ore pulp being prepared more is suitable for
Floating operation, refining effect are more preferable.
Preferably, water further includes the water that separating step obtains.
In the present invention, titanium gypsum dissolved dilution is prepared to the ore pulp of flotation due to going back in flotation step using water
Flotation agent is added, so the water water that also optional separating step obtains.
As further technical solution, in flotation step, flotation agent is added into the ore pulp sized mixing, is uniformly mixed,
It carries out flotation and obtains concentrate foam and tailing ore pulp.
In the present invention, the surface that can be adsorbed on bubble after flotation agent is in conjunction with gypsum, is separated in the form of foam
Come.Concentrate foam and foam-like tailing are obtained after flotation.
As further technical solution, capturing agent include neopelex, lauryl sodium sulfate, enuatrol and
At least one of sodium salicylate.
It is understood that the present invention is not particularly limited the concrete type of the capturing agent, including but not limited to ten
At least one of dialkyl benzene sulfonic acids sodium, lauryl sodium sulfate, enuatrol and sodium salicylate or those skilled in the art
The well known other kinds of capturing agent with above-mentioned substance with similarity.
Preferably, the mass ratio of the additional amount of capturing agent and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000.It is typical but non-limiting, such as the mass ratio of capturing agent and titanium gypsum can be 0.3:1000,0.5:1000,0.7:
1000,0.9:1000,1.1:1000,1.3:1000,1.5:1000,1.7:1000,1.9:1000 or 2:1000.
By the further adjustment and optimization to capturing agent and titanium gypsum mass ratio, the flotation effect of titanium gypsum is improved.
Preferably, foaming agent includes at least one of terpinol, camphorated oil, pinke needle oil and butyl ether oil.
It is understood that the present invention is not particularly limited the concrete type of the foaming agent, it is including but not limited to loose
At least one of oleyl alcohol, camphorated oil, pinke needle oil and butyl ether oil well known to those skilled in the art have with above-mentioned substance
The other kinds of foaming agent of similarity.
Preferably, the mass ratio of the additional amount of foaming agent and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000.It is typical but non-limiting, such as the mass ratio of foaming agent and titanium gypsum can be 0.3:1000,0.5:1000,0.7:
1000,0.9:1000,1.1:1000,1.3:1000,1.5:1000,1.7:1000,1.9:1000 or 2:1000.
By the further adjustment and optimization to foaming agent and titanium gypsum mass ratio, the flotation effect of titanium gypsum is improved.
Preferably, dispersing agent include in ethyl alcohol, waterglass, calcium stearate, calgon, cellulose and glycerol at least
It is a kind of.
It is understood that the present invention is not particularly limited the concrete type of the dispersing agent, including but not limited to second
At least one of alcohol, waterglass, calcium stearate, calgon, cellulose and glycerol or those skilled in the art are known
With above-mentioned substance have similarity other kinds of dispersing agent.
Preferably, the mass ratio of the additional amount of dispersing agent and ore pulp is 1~10:1000.It is typical but non-limiting, such as
The mass ratio of dispersing agent and ore pulp can be 1:1000,2:1000,3:1000,4:1000,5:1000,6:1000,7:1000,8:
1000,9:1000 or 10:1000.
By the further adjustment and optimization to dispersing agent and ore pulp mass ratio, the flotation effect of titanium gypsum is improved.
Preferably, activator includes at least one of sulfuric acid, sulfurous acid, oxalic acid and sodium carbonate.
It is understood that the present invention is not particularly limited the concrete type of the activator, including but not limited to sulphur
At least one of acid, sulfurous acid, oxalic acid and sodium carbonate or it is well known to those skilled in the art have with above-mentioned substance it is similar
The other kinds of activator of property.
Preferably, the mass ratio of the additional amount of activator and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000.It is typical but non-limiting, such as the mass ratio of activator and titanium gypsum can be 0.3:1000,0.5:1000,0.7:
1000,0.9:1000,1.1:1000,1.3:1000,1.5:1000,1.7:1000,1.9:1000 or 2:1000.
By the further adjustment and optimization to activator and titanium gypsum mass ratio, the flotation effect of titanium gypsum is improved.
Preferably, inhibitor includes at least one of vulcanized sodium, lime, dextrin and starch.
It is understood that the present invention is not particularly limited the concrete type of the inhibitor, including but not limited to sulphur
Changing at least one of sodium, lime, dextrin and starch or well known to those skilled in the art and above-mentioned substance has similarity
The other kinds of inhibitor of matter.
Preferably, the mass ratio of the additional amount of inhibitor and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000.It is typical but non-limiting, such as the mass ratio of inhibitor and titanium gypsum can be 0.3:1000,0.5:1000,0.7:
1000,0.9:1000,1.1:1000,1.3:1000,1.5:1000,1.7:1000,1.9:1000 or 2:1000.
By the further adjustment and optimization to inhibitor and titanium gypsum mass ratio, the flotation effect of titanium gypsum is improved.
Preferably, pH regulator includes at least one of sulfuric acid, hydrochloric acid, sodium hydroxide and calcium hydroxide.
It is understood that the present invention is not particularly limited the concrete type of the pH regulator, including but not limited to
At least one of sulfuric acid, hydrochloric acid, sodium hydroxide and calcium hydroxide or well known to those skilled in the art and above-mentioned substance have
There is the other kinds of pH regulator of similarity.
Preferably, the pH of ore pulp is adjusted to 6~8 using pH regulator.At this ph, capturing agent can be more preferable with gypsum
Ground combines, and is conducive to flotation.
It should be noted that the present invention is to above-mentioned capturing agent, foaming agent, dispersing agent, activator, inhibitor and pH regulator
Source there is no special limitation, using each raw material well-known to those skilled in the art, can such as use its commercially available quotient
Product can also voluntarily be prepared using preparation method well known to those skilled in the art.
As further technical solution, flotation is a flotation or multiple flotation.
In the present invention, flotation step can carry out repeatedly.First in flotation early period by the way that a small amount of flotation agent pair is added
Ore pulp carries out flotation, obtains the gypsum of high-purity, then in the flotation later period, by continuing to add flotation agent for remaining a small amount of stone
Cream flotation is clean, to obtain the rich iron charge of higher amount.
As further technical solution, being uniformly mixed as by churned mechanically mode in size mixing step and flotation step
It is uniformly mixed.In step of sizing mixing, titanium gypsum will be sufficiently mixed uniformly with water, otherwise will affect next flotation effect；?
In floatation process, ore pulp will be sufficiently mixed uniformly with flotation agent, avoid gypsum flotation insufficient.
As further technical solution, in separating step, the concentrate foam and tailing ore pulp for respectively obtaining flotation are carried out
It is separated by solid-liquid separation, obtains gypsum and rich iron charge.
In the present invention, the concentrate foam containing dihydrate gypsum and the tail containing metal impurities have been obtained after flotation
Mine ore pulp, the two contain a large amount of liquid, need to remove these liquid.
Preferably, be separated by solid-liquid separation includes at least one of sedimentation, filtering and centrifugation.Separation of solid and liquid generallys use physics point
From.
It preferably, further include drying steps after solid-liquid separation step.After concentrate foam and tailing ore pulp are separated by solid-liquid separation
Most moisture can be removed, but still has a small amount of moisture residue, will be obtained after these extra moisture dryings removals
Purify gypsum and rich iron charge.
Excessive limitation is not done for dry concrete operation method and operating condition such as temperature etc., those skilled in the art can
To carry out selective regulation according to the actual situation.
As further technical solution, isolated water returns to step cycle use of sizing mixing.
In the present invention, by water that concentrate foam and tailing solid-liquid separation on ore pulp obtain containing being added in floatation process
Flotation agent can return to step cycle use of sizing mixing, it is possible to reduce the dosage of water and flotation agent in titanium gypsum purification process reduces titanium
The cost for purification of gypsum.
It is preferably carried out in mode in one kind, as shown in Figure 1, first mixing titanium gypsum according to certain volume ratio with water
Uniformly, it is tuned into ore pulp, flotation agent is then added into ore pulp, is uniformly mixed, flotation is carried out and obtains concentrate foam and tailing ore pulp,
Finally concentrate foam and tailing ore pulp that flotation obtains are filtered, obtain purification gypsum and rich iron charge.
According to the second aspect of the invention, the present invention provides a kind of gypsum that the method for purification using titanium gypsum obtains.
The gypsum is obtained using cheap titanium gypsum as feedstock purification, excessively cannot be rehoused and be utilized and draw to alleviate titanium gypsum
The problem of playing the wasting of resources and environmental pollution.
According to the third aspect of the invention we, the application the present invention provides a kind of gypsum in construction material.The present invention mentions
The gypsum of confession, the purity is high of the dihydrate gypsum contained can substitute the natural gypsum as construction material completely.
The present invention is further illustrated below by specific embodiment and comparative example, it should be understood, however, that, these implementations
Example, which is only used for being described in more detail, to be used, and but should not be understood as present invention is limited in any form.
Titanium gypsum used in the embodiment of the present invention is provided by certain southwestern titanium powder plant, and main chemical compositions are as shown in table 1, with
SO3Meter is secondly water gypsum content is about 75%.Its content of vanadium is higher than 2%, has higher utility value, while also iron content, titanium etc.
Using ingredient.However sulfur content it is higher inhibit its return on a large scale factory utilization.
1 calcium method tailings in vanadium extraction main component of table
Embodiment 1
A kind of method of purification of titanium gypsum is present embodiments provided, as shown in Figure 1, comprising the following steps:
Above-mentioned titanium gypsum 50g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, and 1.5L water is added, stirs evenly；
Then 10mL alcohol is added, air agitation 2min adds 0.1g enuatrol, continues to stir 1min, flotation to non-foam generates；
Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing slurry filtration, drying respectively.
Embodiment 2
Present embodiments provide a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 75g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, and 1.5L water is added, stirs evenly；
Then 5mL waterglass is added, air agitation 2min adds 0.1g lauryl sodium sulfate, continues to stir 1min, flotation to nothing
Foam generates；The finally centrifugation of concentrate foam and tailing ore pulp, the drying to obtaining respectively, obtains gypsum and rich iron charge.
Embodiment 3
Present embodiments provide a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 150g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then 0.2mL butyl ether oil is added, air agitation 2min adds 0.1g lauryl sodium sulfate, continues to stir 1min, float
Choosing to non-foam generates；The finally centrifugation of concentrate foam and tailing ore pulp, the drying to obtaining respectively, obtains gypsum and rich iron charge.
Embodiment 4
Present embodiments provide a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 300g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then 0.2g sodium carbonate is added, air agitation 2min adds 0.1g lauryl sodium sulfate, continues to stir 1min, flotation
It is generated to non-foam；Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing settling ore pulp, drying respectively.
Embodiment 5
A kind of method of purification of titanium gypsum is present embodiments provided, as shown in Figure 1, comprising the following steps:
Above-mentioned titanium gypsum 350g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then hydrochloric acid and sodium hydroxide is added, the pH of solution is adjusted to 6~8, add, 5mL waterglass, 0.2mL butyl ether oil, 0.2g carbon
Sour sodium and 0.2g starch, air agitation 2min add 0.1g lauryl sodium sulfate, continue to stir 1min, flotation is to still
Foam generates；Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing slurry filtration, drying respectively.
Embodiment 6
A kind of method of purification of titanium gypsum is present embodiments provided, as shown in Figure 1, comprising the following steps:
Above-mentioned titanium gypsum 100g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then 5mL waterglass is added, air agitation 2min adds 0.1g neopelex, continues to stir 1min, float
Choosing to non-foam generates；Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing slurry filtration, drying respectively.
Embodiment 7
Present embodiments provide a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 100g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, and 1.5L water, air agitation is added
Then 0.1g neopelex is added in 2min, continue to stir 1min, flotation to non-foam generates；Finally respectively to
The centrifugation of concentrate foam and tailing ore pulp, the drying arrived, obtain gypsum and rich iron charge.
Embodiment 8
Present embodiments provide a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 200g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even, 0.05g neopelex is then added, continues to stir 1min, flotation to non-foam generates, respectively to obtained essence
Mine foam and tailing slurry filtration, drying obtain a flotation gypsum, then 0.05g detergent alkylate sulphur is added into flotation cell
Sour sodium, flotation to bubble-free generate, and filter respectively, are dried to obtain secondary flotation gypsum and rich iron tailings.
Comparative example 1
This comparative example provides a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 400g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then 5mL waterglass is added, air agitation 2min adds 0.1g lauryl sodium sulfate, continues to stir 1min, flotation
It is generated to non-foam；Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing slurry filtration, drying respectively.
Comparative example 2
This comparative example provides a kind of method of purification of titanium gypsum, comprising the following steps:
Above-mentioned titanium gypsum 100g is weighed first to be placed in XFD-1.5 type single-channel type flotation cell, 1.5L water is added, and stirring is equal
It is even；Then 5mL waterglass is added, air agitation 2min adds 0.01g lauryl sodium sulfate, continues to stir 1min, flotation
It is generated to non-foam；Gypsum and rich iron charge finally are obtained to obtained concentrate foam and tailing slurry filtration, drying respectively.
Iron in the purity of embodiment 1-8 and comparative example the 1-2 gypsum purified, yield and rich iron charge is contained respectively
Amount, yield are detected, and the results are shown in Table 2.
The content of iron, yield in the purity of 2 gypsum of table, yield and rich iron charge
| Embodiment | Gypsum purity | Gypsum yield | Iron charge iron content | Iron yield |
| Embodiment 1 | 95.3% | 83.1% | 21.4% | 84.6% |
| Embodiment 2 | 91.2% | 86.3% | 20.9% | 85.7% |
| Embodiment 3 | 85.6% | 92.8% | 19.4% | 83.8% |
| Embodiment 4 | 82.5% | 94.7% | 18.7% | 82.4% |
| Embodiment 5 | 81.6% | 95.1% | 18.1% | 81.3% |
| Embodiment 6 | 88.3% | 89.7% | 20.4% | 86.9% |
| Embodiment 7 | 85.1% | 92.5% | 28.2% | 70.1% |
| Embodiment 8 is primary | 93.1% | - | - | - |
| Embodiment 8 two times | 86.5% | 93.1%* | 27.6% | 75.2% |
| Comparative example 1 | 80.9% | 95.8% | 17.5% | 80.5% |
| Comparative example 2 | 93.6% | 32.8% | 8.9% | 92.5% |
*: indicating the accumulative yield of flotation twice
Embodiment 2 and the difference of comparative example 1 be, the titanium gypsum of comparative example 1 and the ratio of water are greater than the titanium stone of embodiment 2
The ratio of cream and water.From table 2 it can be seen that the purity that embodiment 2 purifies obtained gypsum is substantially better than the gypsum of comparative example 1
Purity.When titanium gypsum is mixed with water, the additive amount of water cannot be too small, should control in a certain range.
Embodiment 6 is identical as the additional amount of 7 capturing agent of embodiment, but dispersing agent waterglass is not added in embodiment 7.From
Table 2 is as can be seen that the purity that embodiment 6 purifies obtained gypsum is substantially better than the purity of the gypsum of embodiment 7.Illustrate dispersing agent
Addition be more conducive to the purification of titanium gypsum.
Embodiment 6 and the difference of comparative example 2 are that the additional amount of capturing agent is significantly less than catching for embodiment 6 in comparative example 2
Obtain the additional amount of agent.From table 2 it can be seen that embodiment 6 purifies the gypsum receipts that obtained gypsum yield is substantially better than comparative example 2
Rate.The additional amount of capturing agent cannot be too small, should control in a certain range.
Titanium gypsum in embodiment 8 have passed through purification by floatation twice, from table 2 it can be seen that mentioning after second of flotation
The purity of pure obtained gypsum is significantly improved.
Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: its according to
So be possible to modify the technical solutions described in the foregoing embodiments, or to some or all of the technical features into
Row equivalent replacement；And these are modified or replaceed, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method of purification of titanium gypsum, which is characterized in that including sizing mixing, flotation and separation；
Wherein, in the flotation step, used flotation agent includes capturing agent, optional foaming agent, optional dispersing agent, appoints
The activator of choosing, optional inhibitor and optional pH regulator.
2. the method for purification of titanium gypsum according to claim 1, which is characterized in that, will be to be processed in the step of sizing mixing
Titanium gypsum and water according to mass ratio be that 1:3~20 are uniformly mixed；
Preferably, in the step of sizing mixing, titanium gypsum to be processed is uniformly mixed with water according to mass ratio for 1:5~10；
Preferably, the water further includes the water that separating step obtains.
3. the method for purification of titanium gypsum according to claim 1, which is characterized in that in the flotation step, to sizing mixing
To ore pulp in add flotation agent, be uniformly mixed, carry out flotation obtain concentrate foam and tailing ore pulp.
4. the method for purification of titanium gypsum according to claim 1-3, which is characterized in that the capturing agent includes ten
At least one of dialkyl benzene sulfonic acids sodium, lauryl sodium sulfate, enuatrol and sodium salicylate；
Preferably, the mass ratio of the additional amount of the capturing agent and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000；
Preferably, the foaming agent includes at least one of terpinol, camphorated oil, pinke needle oil and butyl ether oil；
Preferably, the mass ratio of the additional amount of the foaming agent and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000；
Preferably, the dispersing agent include in ethyl alcohol, waterglass, calcium stearate, calgon, cellulose and glycerol at least
It is a kind of；
Preferably, the mass ratio of the additional amount of the dispersing agent and ore pulp is 1~10:1000；
Preferably, the activator includes at least one of sulfuric acid, sulfurous acid, oxalic acid and sodium carbonate；
Preferably, the mass ratio of the additional amount of the activator and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000；
Preferably, the inhibitor includes at least one of vulcanized sodium, lime, dextrin and starch；
Preferably, the mass ratio of the additional amount of the inhibitor and titanium gypsum be 0.3~2:1000, preferably 0.5~1.2:
1000；
Preferably, the pH regulator includes at least one of sulfuric acid, hydrochloric acid, sodium hydroxide and calcium hydroxide；
Preferably, the pH of ore pulp is adjusted to 6~8 using pH regulator.
5. the method for purification of titanium gypsum according to claim 1, which is characterized in that the flotation is a flotation or more
Secondary flotation.
6. the method for purification of titanium gypsum according to claim 2 or 3, which is characterized in that described to be uniformly mixed to pass through machine
The mode of tool stirring is uniformly mixed.
7. the method for purification of titanium gypsum according to claim 1, which is characterized in that in the separating step, will float respectively
It selects obtained concentrate foam and tailing ore pulp to be separated by solid-liquid separation, obtains gypsum and rich iron charge；
Preferably, described be separated by solid-liquid separation includes at least one of sedimentation, filtering and centrifugation；
It preferably, further include drying steps after the solid-liquid separation step.
8. the method for purification of titanium gypsum according to claim 1, which is characterized in that the isolated water return is sized mixing
Step cycle uses.
9. the gypsum obtained using the method for purification of the described in any item titanium gypsums of claim 1-8.
10. gypsum or gypsum as claimed in claim 9 that the method for purification of the described in any item titanium gypsums of claim 1-8 obtains
Application in construction material.
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| CN112279288A (en) * | 2020-11-04 | 2021-01-29 | 湖南振亚新材料科技有限公司 | Continuous preparation method of modified calcium sulfate |
| CN115180646A (en) * | 2022-08-22 | 2022-10-14 | 清华大学 | Method for purifying calcium sulfate dihydrate from by-product gypsum |
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