CN110316708A - The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum - Google Patents
The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum Download PDFInfo
- Publication number
- CN110316708A CN110316708A CN201910491974.7A CN201910491974A CN110316708A CN 110316708 A CN110316708 A CN 110316708A CN 201910491974 A CN201910491974 A CN 201910491974A CN 110316708 A CN110316708 A CN 110316708A
- Authority
- CN
- China
- Prior art keywords
- gypsum
- phosphoric acid
- slurry
- half water
- type high
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
- C01B25/228—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen one form of calcium sulfate being formed and then converted to another form
-
- 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
- C01F11/466—Conversion of one form of calcium sulfate to another
-
- 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
-
- 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
-
- 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
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- 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
-
- 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
- C01P2006/82—Compositional purity water content
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to the methods that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum, belong to Wet-process Phosphoric Acid Production technical field.Present invention solves the technical problem that being that existing wet method phosphoric acid manufacture process cannot obtain the high-strength αsemiwatergypsum of function admirable while high-concentration phosphoric acid is made.The invention discloses the methods that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is first reacted with mixture of sulfuric phosphoric acid with phosphorus ore and phosphoric acid and semi-hydrated gypsum is made, half water phosphoric acid product of high concentration and thick semi-hydrated gypsum are obtained after filtering, thick semi-hydrated gypsum generates αsemiwatergypsum by recrystallization twice, is finally filtered, washed, dries to obtain alpha type high-strength gypsum.The present invention has also carried out decolorization during the reaction, and obtained alpha type high-strength gypsum whiteness is whiter.The present invention is whole, and low energy consumption, good in economic efficiency.
Description
Technical field
The invention belongs to Wet-process Phosphoric Acid Production technical fields, and in particular to phosphorus ore produces the half high-strength stone of water phosphoric acid coproducing alpha type
The method of cream.
Background technique
Phosphoric acid by wet process is the method with inorganic acid decomposing phosphate rock stone preparing phosphoric acid, and most common inorganic acid is sulfuric acid, sulfuric acid
Legal system phosphoric acid can generate a large amount of ardealite, according to gypsum crystallization hydration object difference, and be divided into two Water flow-paths, half Water flow-path,
Anhydrous process, industrialized only two water and half Water flow-path are especially the most universal with two Water flow-paths.Two Water flow-path technologies at
It is ripe, simple process, but phosphoric acid concentration is lower, and often needing to be concentrated could be used to produce phosphate product；And dihydrate gypsum does not have glue
Solidifying property, cannot directly be used as building materials, can only obtain the poor beta-type semi-hydrated gypsum powder of performance after calcining, and the intensity of gypsum is low,
Limit the use of ardealite.Therefore a large amount of ardealite can only be banked up as solid waste.The year of China's ardealite at present
Discharge amount is more than 70,000,000 tons, and comprehensive utilization ratio only has 20% or so, and adding up volume of cargo in storage is more than 300,000,000 tons.The heap of a large amount of ardealites
Not only land occupation is deposited, also polluted environment, limits the benign sustainable development of sulphur dioxide of phosphor chemical industry.
102674279 A of Chinese patent CN discloses a kind of method of producing phosphoric acid by hemihydrate technique, which is to pass through control
The molar ratio of the CaO in sulfuric acid and ground phosphate rock in overfall processed carries out pre-reaction, then plus sulfuric acid control acid solution in sulfate radical content
It is 1.5~2.0%, sufficiently reaction forms semi-hydrated gypsum crystallization, and filtering slurry obtains half water phosphoric acid of high concentration and semi-hydrated gypsum.It should
It is low that method solves two Water flow-paths production phosphoric acid concentration, the high problem of energy consumption, but the semi-hydrated gypsum phosphor fluorine containing impurity of by-product is higher,
Crystalline form is poor, and physical property is poor, is still difficult to be utilized.
105253867 A of Chinese patent CN discloses a kind of production method of phosphoric acid by wet process by-product αsemiwatergypsum.The hair
Bright reacted with dilute sulfuric acid and phosphorus ore, and part slurry filtration is taken to obtain phosphate dihydrate, and dihydrate gypsum and remaining slurry, which enter, turns crystalline substance
Slot adds sulfuric acid and crystal modifier to produce αsemiwatergypsum.The problem for the ardealite performance difference that the invention effectively solves, but produced α half
The whiteness of water gypsum is lower, it is difficult to meet high-end market demand, crystal modifier is added to also increase cost and control difficulty；And produced phosphorus
Acid is still low concentration phosphoric acid, and needing to be concentrated could use, and energy consumption is higher.
Summary of the invention
Technical problems to be solved of the present invention are that existing wet method phosphoric acid manufacture process cannot be in obtained high-concentration phosphoric acid
The high-strength αsemiwatergypsum of function admirable is obtained simultaneously.
Technical proposal that the invention solves the above-mentioned problems is to provide phosphorus ore and produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type
Method includes the following steps:
(1) the mixed slurry B that half water phosphoric acid and semi-hydrated gypsum is made is reacted with phosphorus ore using mixture of sulfuric phosphoric acid；
(2) half water phosphoric acid product of high concentration and thick semi-hydrated gypsum C are obtained after filtering to above-mentioned mixed slurry B；
(3) thick semi-hydrated gypsum C is converted under the conditions of a certain concentration mixture of sulfuric phosphoric acid and temperature by recrystallizing reactive moieties
Dihydrate gypsum obtains slurry D；
(4) slurry D continues recrystallization reaction life under conditions of mixture of sulfuric phosphoric acid concentration and temperature are above step (3)
At αsemiwatergypsum, slurry E is obtained；
(5) slurry E is filtered, washed, dries to obtain alpha type high-strength gypsum.
Wherein, at 85~100 DEG C, the liquid-solid ratio of mixed slurry B is controlled in 2-10 the control of step (1) reaction temperature.
Wherein, the control of step (3) reaction temperature is at 40~70 DEG C；In liquid nitration mixture contained by slurry D based on mass fraction
P2O5For 1%~10%, SO4 2-Content is 1%~8%.
Further, the crystal water content mass fraction of gypsum is 12%~18% in rate-determining steps (3) slurry D.Sulfuric acid
Calcium can be combined together to form crystal with water, and non-liquid water of this part in conjunction with calcium sulfate is called the crystallization water.
Wherein, the control of step (4) reaction temperature is at 80~100 DEG C；In liquid nitration mixture contained by slurry E based on mass fraction
P2O5For 13%~30%, SO4 2-Content is 12%~25%.
Wherein, the phosphorus ore Powder Particle Size < 0.5mm in step (1), based on mass fraction moisture < 15%, after drying moisture content
Siccative, that is, butt based on mass fraction burn vector < 10%, SiO2< 12%, MgO < 3%, BPL > 65%.Wherein butt refers to
Siccative after drying materials moisture content.
Further, grey black foam A is scraped in step (1) reaction process, until slurry surface without black foam, obtains
Mixed slurry B.
Further, step (3) recrystallization process is added hydrogen peroxide and carries out decolorization.
The present invention further discloses the method that phosphorus ore produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type, includes the following steps:
(1) concentrated sulfuric acid, half water phosphoric acid of part, filtrate F, ground phosphate rock are added in reactor R1 and are reacted, control reaction
It 85~100 DEG C of temperature, is stirred to react 2~8 hours, obtains slurry B；
(2) slurry B is squeezed into filter X1 filtering, isolates half water phosphoric acid and thick semi-hydrated gypsum C, half water phosphoric acid separates portion
Divide Returning reactor R1 to be recycled, partially enters reactor R3 and use；
(3) thick semi-hydrated gypsum C, gypsum wash water H are added in reactor R2 and carry out recrystallization reaction, control reaction temperature 40
It~70 DEG C, is stirred to react 1~4 hour, obtains slurry D；
(4) half water phosphoric acid of part, the concentrated sulfuric acid obtained by step (2), slurry D are added in reactor R3 and recrystallize instead
It answers, controls 80~100 DEG C of reaction temperature, be stirred to react 1~6 hour, obtain slurry E；
(5) slurry E is squeezed into filter X2 filtering, isolates filtrate F and gypsum filter cake, gypsum filter cake is washed with hot water
To gypsum wash water H and gypsum wet feed G, filtrate F Returning reactor R1 is recycled, and gypsum wash water H Returning reactor R2 circulation makes
With, by gypsum wet feed G be sent into dryer M1 drying, obtain the high-strength white gypsum of the higher α type of whiteness.
Wherein, the concentrated sulfuric acid, half water phosphoric acid of part, filtrate F, ground phosphate rock 0.2~0.8:1 in mass ratio~2:2 in step (1)
~10:1, which is added in reactor R1, to be reacted.
Wherein, thick semi-hydrated gypsum C, gypsum wash water H 1:0.5 in mass ratio~3 are added in reactor R2 and carry out by step (3)
Recrystallization reaction.
Wherein, half water phosphoric acid of step (4) part, the concentrated sulfuric acid, slurry D are that reactor is added in 1~5:1~3:10 in mass ratio
Recrystallization reaction is carried out in R3.
Wherein, step (3) recrystallization process is added hydrogen peroxide and carries out decolorization, thick semi-hydrated gypsum C and hydrogen peroxide, gypsum
Wash water H 1:0.01~0.05:0.5 in mass ratio~3, which is added in reactor R2, to be reacted.
Beneficial effects of the present invention:
The present invention first uses the half water phosphoric acid and thick semi-hydrated gypsum of conventional hemihydrate technique output high concentration, then by twice
The poor thick semi-hydrated gypsum of performance is first converted dihydrate gypsum by recrystallization process, then from dihydrate gypsum be converted into crystalline form it is good,
The αsemiwatergypsum of function admirable, therefore the present invention can obtain function admirable, purity is high while obtained high concentration phosphorus acid product
High-strength αsemiwatergypsum, wherein high concentration phosphorus acid product contains P based on mass fraction2O5For 35%~45%, contain SO4 2-It is 1.0%
~3.0%；
The present invention allows thick semi-hydrated gypsum part aquation in hydration process (i.e. first time recrystallization process), retains semi-hydrated gypsum
Crystal seed of the nucleus as second recrystallization, while using in phosphoric acid by wet process per se with SO4 2-、K+、Na+、Mg2+、Al3+、
Fe3+Plasma plays good induction modification to gypsum crystalline form, and draw ratio 1~5 can be formed by not needing addition crystal modifier
Between short cylinder αsemiwatergypsum, reduce costs；
The present invention during the reaction scrapes foam, has effectively removed the grey black organic matter in ardealite, remaining
The greyish black colored foreign in part, using the strong oxidizing property of hydrogen peroxide, remaining greyish black colored foreign is bleached, most by the way that hydrogen peroxide is added
So that gypsum is decolourized eventually, obtains the higher gypsum of whiteness；
Reaction process of the present invention by the part concentrated sulfuric acid in secondary recrystallization is added, and is provided using the heat of dilution of the concentrated sulfuric acid
Heat needed for recrystallization process, at the same the raising of sulfuric acid content also reduce recrystallization process needed for temperature, therefore tie again
Brilliant process does not need external heat source, has saved heating cost, while also reducing conventional extraction slot slurry and dodging cold energy consumption, comprehensive
Better economic benefit.
Detailed description of the invention
Fig. 1 is the process flow diagram that phosphorus ore of the present invention produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type.
Specific embodiment
The present invention provides the method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum, includes the following steps:
(1) the mixed slurry B that half water phosphoric acid and semi-hydrated gypsum is made is reacted with phosphorus ore using mixture of sulfuric phosphoric acid；
(2) half water phosphoric acid product of high concentration and thick semi-hydrated gypsum C are obtained after being filtered to slurry B；
(3) thick semi-hydrated gypsum C is converted under the conditions of a certain concentration mixture of sulfuric phosphoric acid and temperature by recrystallizing reactive moieties
Dihydrate gypsum obtains slurry D；
(4) slurry D continues recrystallization reaction life under conditions of mixture of sulfuric phosphoric acid concentration and temperature are above step (3)
At αsemiwatergypsum, slurry E is obtained；
(5) slurry E is filtered, washed, dries to obtain the high-strength white gypsum of α type.
Wherein, at 85~100 DEG C, the liquid-solid ratio of mixed slurry B is controlled in 2-10 the control of step (1) reaction temperature.
Wherein, the control of step (3) reaction temperature is at 40~70 DEG C；In liquid nitration mixture contained by slurry D based on mass fraction
P2O5For 1%~10%, SO4 2-Content is 1%~8%.
Further, the crystal water content mass fraction of gypsum is 12%~18% in rate-determining steps (3) slurry D.
Wherein, the control of step (4) reaction temperature is at 80~100 DEG C；In liquid nitration mixture contained by slurry E based on mass fraction
P2O5For 13%~30%, SO4 2-Content is 12%~25%.
The present invention provides the method that phosphorus ore produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type, specifically can be in accordance with the following steps
It carries out:
(1) concentrated sulfuric acid, half water phosphoric acid of part, filtrate F, ground phosphate rock 0.2~0.8:1 in mass ratio~2:2~10:1 are added
Enter and reacted in reactor R1, controls 85~100 DEG C of reaction temperature, be stirred to react 2~8 hours, scrape reactor top
Grey black foam A, obtains slurry B；
(2) slurry B is squeezed into filter X1 filtering, isolates half water phosphoric acid and thick semi-hydrated gypsum C, half water phosphoric acid separates portion
Divide Returning reactor R1 to be recycled, partially enters reactor R3 and use；
(3) thick semi-hydrated gypsum C is reacted with hydrogen peroxide, gypsum wash water H 1:0.01~0.05:0.5 in mass ratio~3 addition
It is reacted in device R2, controls 40~70 DEG C of reaction temperature, be stirred to react 1~4 hour, obtain slurry D；
It (4) is in mass ratio that 1~5:1~3:10 is added instead by half water phosphoric acid of part, the concentrated sulfuric acid, slurry D obtained by step (2)
It answers and is reacted in device R3, control 80~100 DEG C of reaction temperature, be stirred to react 1~6 hour, obtain slurry E；
(5) slurry E is squeezed into filter X2 filtering, isolates filtrate F and gypsum filter cake, gypsum filter cake is washed with hot water
To gypsum wash water H and gypsum wet feed G, filtrate F Returning reactor R1 is recycled, and gypsum wash water H Returning reactor R2 circulation makes
With, by gypsum wet feed G be sent into dryer M1 drying, obtain the high-strength white gypsum of the higher α type of whiteness.
The invention mainly relates to chemical equation it is as follows:
In reactor R1:
Ca5F(PO4)3+7H3PO4=5Ca (H2PO4)2+HF↑
2Ca(H2PO4)2+2H2SO4+H2O=2Ca SO4·0.5H2O↓+4H3PO4
In reactor R2:
Ca SO4·0.5H2O+1.5H2O=Ca SO4·2H2O
In reactor R3:
Ca SO4·2H2O=Ca SO4·0.5H2O+1.5H2O
The mechanism that the present invention can be mutually converted at different conditions using the different hydrates of gypsum is different by controlling
The poor thick semi-hydrated gypsum of performance is first converted dihydrate gypsum by liquid-phase condition, then is converted into from dihydrate gypsum that crystalline form is good, property
The excellent αsemiwatergypsum of energy.By recrystallization process twice, the impurity in thick semi-hydrated gypsum is sufficiently discharged, half water of product α
The purity is high of gypsum, impurity is few, best in quality, while having recycled the resources such as phosphorus, fluorine.
The present invention is in hydration process (i.e. first time recrystallization process) by containing to crystal water of gypsum in step (3) slurry D
The control of amount, allows thick semi-hydrated gypsum part aquation, retains crystal seed of the nucleus of semi-hydrated gypsum as second of recrystallization, while benefit
With in phosphoric acid by wet process per se with SO4 2-、K+、Na+、Mg2+、Al3+、Fe3+Plasma plays good induction to gypsum crystalline form
Modification does not need the short cylinder αsemiwatergypsum that addition crystal modifier can be formed between draw ratio 1~5, reduces costs.
During phosphorus ore preparing phosphoric acid, a large amount of grey black foam can be generated, and these foams are mainly that black is organic
Object is formed, and traditional method is to add defoaming agent, and foam is allowed to dissolve, and is entered in gypsum after filtering, causes gypsum in grey black.This
Invention is low using foam volume density, largely floats on the characteristic on slurry face, during the reaction scrapes foam, i.e., effectively
Eliminate the grey black organic matter in ardealite.Further, the greyish black colored foreign in the part of final residual, by the way that dioxygen is added
Remaining greyish black colored foreign is bleached using the strong oxidizing property of hydrogen peroxide, finally gypsum is made to decolourize, it is higher to obtain whiteness by water
Gypsum.
During traditional preparing phosphoric acid, extraction tank, the heat of dilution and phosphorus of the concentrated sulfuric acid is all usually added in the concentrated sulfuric acid
Heat that ore decomposition is discharged is added so that reaction slurry temperature is excessively high, to control reaction temperature it is necessary to by dodge it is cold come pair
Slurry cooling, the heat for needing to remove is more, so the energy consumption for dodging cold process is also higher.The present invention is by the part concentrated sulfuric acid secondary
The reaction process of recrystallization is added, heat needed for recrystallization process is provided using the heat of dilution of the concentrated sulfuric acid, sulfuric acid content
Temperature needed for raising also reduces recrystallization process, therefore recrystallization process does not need external heat source, has saved heating cost,
Also reducing extraction tank slurry dodges cold energy consumption simultaneously, and overall economic efficiency is preferable.
In order to obtain better effect, phosphorus ore Powder Particle Size < 0.5mm of the present invention, moisture < 15%, is done based on mass fraction
Base based on mass fraction burn vector < 10%, SiO2< 12%, MgO < 3%, BPL > 65%.
In order to obtain better effect, step (1) of the present invention first the concentrated sulfuric acid and circulation filtrate acid F and acid reflux can be added mixed
It is flowed into reactor R1 after being premixed in sour device 1, then ground phosphate rock is added into reactor R1, step (4) can be first by half water phosphorus of part
Acid and the concentrated sulfuric acid be added acid mixing device 2 in premix after, then flow into reactor R3 with slurry D hybrid reaction.
The concentrated sulfuric acid used in the present invention is technical grade sulfuric acid, >=98%H2SO4。
The present invention will be further explained and explanation with comparative example by the following examples.
Embodiment 1
Phosphorus ore used in the present embodiment is the phosphorus concentrate that the phosphorus ore of Fuquan, Guizhou mining area extraction obtains after flotation, chemistry
Component by mass percentage, P2O5: 33.76%, CaO:48.29%, MgO:1.15%, SiO2: 9.83%, fineness is with quality
Percentages, 100%, -100 mesh 92.36% of -32 mesh (< 0.5mm).
The present embodiment produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type using phosphorus ore, the specific steps are as follows:
(1) be configured to mixture of sulfuric phosphoric acid 1 with phosphoric acid enriching sulfuric acid and water, chemical constituent by mass percentage, P2O5: 29%,
SO4 2-: 15%, phosphorus concentrate, mixture of sulfuric phosphoric acid 1 and concentrated sulfuric acid 1:3.5:0.3 in mass ratio are added in reactor R1, are stirred to react 3
Hour, 92~95 DEG C of reaction temperature, black foam A is constantly scraped in reaction process, until slurry surface without black foam, obtains
Slurry B；
(2) slurry B is filtered, obtains half water phosphoric acid and thick semi-hydrated gypsum C；
(3) be configured to mixture of sulfuric phosphoric acid 2 with phosphoric acid enriching sulfuric acid and water, chemical constituent by mass percentage, P2O5: 6%,
SO4 2-: 4%, thick semi-hydrated gypsum C, mixture of sulfuric phosphoric acid 2, the hydrogen peroxide 1:0.7:0.015 in mass ratio that mass concentration is 27% are added
Enter in reactor R2, be stirred to react 1.5 hours, 50 DEG C of reaction temperature, obtains slurry D；
(4) reactor R3 is added in half water phosphoric acid, the concentrated sulfuric acid 10:1.7:1.3 in mass ratio obtained slurry D, step (2)
In, 82~84 DEG C of reaction temperature are controlled, is stirred to react 2 hours, obtains slurry E；
(5) slurry E is filtered, obtains filtrate F, then plus 83 DEG C hot water wash filter cake, obtain wash water H and gypsum wet feed
G, the thick semi-hydrated gypsum C that hot water additional amount is obtained with step (2) is 0.69:1 in mass ratio, and gypsum wet feed G dryer is existed
135~140 DEG C dry 25 minutes, obtain the water-white gypsum of α type half.
The performance indicator for being related to product to the above process detects, and wherein chemical constituent index is that mass percent is dense
Degree, as a result as follows:
Half water phosphoric acid product: P2O5For 41.07%, SO4 2-For 1.38%, MgO 1.41%, K2O is 0.06%, Na2O is
0.13%, Al2O3For 0.35%, Fe2O3It is 0.48%；
The crystal water of gypsum of slurry D: 15.35%；
αsemiwatergypsum product: the crystallization water 5.72%, total P2O5For 0.08%, water-soluble P2O5It is for 0.03%, total F
0.06%, water-soluble F is 0.01%, and whiteness 85.7%, gypsum crystalline form is hexagonal prism body, and draw ratio has 1~3, and gypsum is physical
Mark thick 36% can be detected, it is 6 minutes pre-hardening, final set 8 minutes, 2 hours anti-folding 7.8MPa, over dry resistance to compression 52.1MPa.
Embodiment 2
Phosphorus ore used in the present embodiment is the phosphorus concentrate that the phosphorus ore of Fuquan, Guizhou mining area extraction obtains after flotation, chemistry
Component by mass percentage, P2O5: 34.18%, CaO:48.36%, MgO:1.07%, SiO2: 9.51%, fineness is with quality
Percentages, 100%, -100 mesh 93.82% of -32 mesh (< 0.5mm).
The present embodiment produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type using phosphorus ore, the specific steps are as follows:
(1) filtrate F, the dense sulphur that step (5) obtains in the half water phosphoric acid that is obtained with step (2) in embodiment 1, embodiment 1
Acid, phosphorus concentrate are added in reactor R1, half water phosphoric acid in mass ratio: filtrate F: the concentrated sulfuric acid: phosphorus concentrate=1.5:2.1:0.29:1,
It is stirred to react 3.5 hours, 93~97 DEG C of reaction temperature, black foam A is constantly scraped in reaction process, until slurry surface is without black
Color foam obtains slurry B；
(2) slurry B is filtered, obtains half water phosphoric acid and thick semi-hydrated gypsum C；
(3) by the wash water H of step (5) in the thick semi-hydrated gypsum C of step (2), embodiment 1, mass concentration be 35% it is double
Oxygen water 1:0.7:0.012 in mass ratio is added in reactor R2, is stirred to react 2 hours, 55 DEG C of reaction temperature, obtains slurry D；
(4) half water phosphoric acid, the concentrated sulfuric acid 10:1.8 in mass ratio for obtaining slurry D that step (3) obtains, step (2):
1.3 are added in reactor R3, control 82~84 DEG C of reaction temperature, are stirred to react 2 hours, obtain slurry E；
(5) the slurry E obtained step (4) is filtered, and obtains filtrate F, and then plus 88 DEG C of hot water washs filter cake, is washed
Liquid H and gypsum wet feed G, the thick semi-hydrated gypsum that hot water additional amount is obtained with step (2) is 0.68:1 in mass ratio, by gypsum wet feed
G dryer is dried 25 minutes at 135~140 DEG C, obtains the water-white gypsum of α type half.
The performance indicator for being related to product to the above process detects, and wherein chemical constituent index is that mass percent is dense
Degree, as a result as follows:
Half water phosphoric acid product: P2O5For 40.87%, SO4 2-For 1.55%, MgO 1.35%, K2O is 0.05%, Na2O is
0.11%, Al2O3For 0.29%, Fe2O3It is 0.37%；
The crystal water of gypsum of slurry D: 16.63%.
αsemiwatergypsum product: the crystallization water 5.51%, total P2O5For 0.06%, water-soluble P2O5It is for 0.02%, total F
0.07%, water-soluble F is 0.01%, and whiteness 86.5%, gypsum crystalline form is hexagonal prism body, and draw ratio has 1~2, and gypsum is physical
Mark thick 34% can be detected, it is 7 minutes pre-hardening, final set 10 minutes, 2 hours anti-folding 8.5MPa, over dry resistance to compression 58.9MPa.
Embodiment 3
The present embodiment produces the half high-strength white gypsum of water phosphoric acid coproducing alpha type using phosphorus ore, the specific steps are as follows:
(1) filtrate F, the dense sulphur that step (5) obtains in the half water phosphoric acid that is obtained with step (2) in embodiment 2, embodiment 2
Sour, embodiment 1 phosphorus concentrate is added in reactor R1, half water phosphoric acid in mass ratio: filtrate F: the concentrated sulfuric acid: phosphorus concentrate=1.55:
2.05:0.3:1 is stirred to react 4 hours, and 91~95 DEG C of reaction temperature, black foam A is constantly scraped in reaction process, until material
Surface is starched without black foam, obtains slurry B.
(2) slurry B is filtered, obtains half water phosphoric acid and thick semi-hydrated gypsum C；
(3) by the wash water H of step (5) in the thick semi-hydrated gypsum C of step (2), embodiment 2, mass concentration be 40% it is double
Oxygen water 1:0.7:0.01 in mass ratio is added in reactor R2, is stirred to react 2.5 hours, 58 DEG C of reaction temperature, obtains slurry D；
(4) half water phosphoric acid, the concentrated sulfuric acid 10:1.85 in mass ratio for obtaining slurry D that step (3) obtains, step (2):
1.2 are added in reactor R3, control 84~87 DEG C of reaction temperature, are stirred to react 3 hours, obtain slurry E；
(5) the slurry E obtained step (4) is filtered, and obtains filtrate F, and then plus 85 DEG C of hot water washs filter cake, and hot water adds
Enter the thick semi-hydrated gypsum that amount is obtained with step (2) is 0.69:1 in mass ratio, washing lotion H and gypsum wet feed G is obtained after washing, by stone
Cream wet feed G dryer is dried 25 minutes at 135~140 DEG C, obtains the water-white gypsum of α type half.
The performance indicator for being related to product to the above process detects, and wherein chemical constituent index is that mass percent is dense
Degree, as a result as follows:
Half water phosphoric acid product: P2O5For 41.36%, SO4 2-For 1.48%, MgO 1.49%, K2O is 0.08%, Na2O is
0.16%, Al2O3For 0.39%, Fe2O3It is 0.55%；
The crystal water of gypsum of slurry D: 16.27%.
αsemiwatergypsum product: the crystallization water 5.23%, total P2O5For 0.08%, water-soluble P2O5It is for 0.03%, total F
0.06%, water-soluble F is 0.03%, and whiteness 87.2%, gypsum crystalline form is hexagonal prism body, and draw ratio has 1~2, and gypsum is physical
Mark thick 32% can be detected, it is 6 minutes pre-hardening, final set 8 minutes, 2 hours anti-folding 8.3MPa, over dry resistance to compression 56.5MPa.
Comparative example 1
This comparative example produces half water phosphoric acid and semi-hydrated gypsum with traditional method, the specific steps are as follows:
(1) extraction is added with the phosphorus concentrate 21:1 in mass ratio in step (1) obtains in embodiment 1 slurry B, embodiment 1
It takes in slot and is stirred to react, 92 DEG C of reaction temperature, react the extraction of formation in 1 hour slurry X；
(2) divide 50% to crystallization tank by quality for slurry X, the concentrated sulfuric acid is added, slurry X and the concentrated sulfuric acid press quality in crystallization tank
Ratio is 35:1, is stirred to react, and after 95 DEG C of reaction temperature, reaction 30 minutes, obtains slurry Y；
(3) divide 50% as overfall by quality for slurry Y and return to extraction tank, while phosphorus concentrate being added into extraction tank, return
Starch with phosphorus concentrate is 21:1 in mass ratio, continues extraction reaction, obtains slurry X1 after 92 DEG C of reaction temperature, reaction 1 hour；
(4) divide 50% to crystallization tank by quality for slurry X1, the concentrated sulfuric acid is added, slurry X1 and the concentrated sulfuric acid press matter in crystallization tank
Amount ratio is 35:1, is stirred to react, 95 DEG C of reaction temperature, after reaction 30 minutes, obtains slurry Y1；
(5) slurry Y1 is filtered, obtains half water phosphoric acid M and thick semi-hydrated gypsum P, then plus 85 DEG C hot water wash filter cake,
Hot water additional amount and thick semi-hydrated gypsum P mass ratio are 1:1, obtain semi-hydrated gypsum powder Z after the gypsum after washing is dry.
The performance indicator for being related to product to the above process detects, and wherein chemical constituent index is that mass percent is dense
Degree, as a result as follows:
The chemical index of half water phosphoric acid M: P2O5For 42.02%, SO4 2-It is 1.45%；
Semi-hydrated gypsum powder Z product: the crystallization water 5.42%, total P2O5For 0.87%, water-soluble P2O5It is for 0.33%, total F
0.84%, water-soluble F is 0.17%, whiteness 42.8%, and gypsum crystalline form is that sheet is embedded in the plycrystalline diamond being formed together, plycrystalline diamond diameter
There is 50~70um, gypsum physical property detection mark thick 78% is 45 minutes pre-hardening, and final set 82 minutes, 2 hours anti-folding 0.4MPa, absolutely
Dry resistance to compression 4.9MPa.
This comparative example has produced out half water phosphoric acid and thick semi-hydrated gypsum, the phosphorus fluorine impurity of thick semi-hydrated gypsum with traditional method
Content is high, and crystal morphology is poor, and physical property is poor, and intensity is low, cannot be used as commodity gypsum, can only be stacked in cinder field, causes money
Source waste and risk of environmental pollution.
Comparative example 2
This comparative example produces the method (do not scrape bubble, do not bleach) of half water phosphoric acid coproduction alpha type high-strength gypsum using phosphorus ore, specifically
Steps are as follows:
(1) mixture of sulfuric phosphoric acid and the concentrated sulfuric acid of step (1) in the phosphorus concentrate of step (1) in embodiment 1, embodiment 1 are pressed into matter
Amount is added in reactor R1 than 1:3.5:0.3, is stirred to react 3 hours, 92~95 DEG C of reaction temperature, obtains slurry B；
(2) slurry B is filtered, obtains half water phosphoric acid and thick semi-hydrated gypsum C；
(3) mixture of sulfuric phosphoric acid, the 1:0.71 in mass ratio of step (3) in the thick semi-hydrated gypsum C of step (2), embodiment 1 are added
Enter in reactor R2, be stirred to react 1.5 hours, 50 DEG C of reaction temperature, obtains slurry D；
(4) half water phosphoric acid, the concentrated sulfuric acid 10:1.7:1.3 in mass ratio that step (3) obtains slurry D, step (1) obtain
It is added in reactor R3, controls 82~84 DEG C of reaction temperature, be stirred to react 2 hours, obtain slurry E；
(5) the slurry E obtained step (4) is filtered, and obtains filtrate F, and then plus 83 DEG C of hot water washs filter cake, is washed
Liquid H and gypsum wet feed G, the thick semi-hydrated gypsum 0.7:1 in mass ratio that hot water additional amount is obtained with step (1) is added, and gypsum is wet
Alpha type high-strength gypsum is obtained after material G is dry.
The performance indicator for being related to product to the above process detects, and wherein chemical constituent index is that mass percent is dense
Degree, as a result as follows:
Half water phosphoric acid product: P2O5For 40.96%, SO4 2-For 1.42%, MgO 1.37%, K2O is 0.07%, Na2O is
0.15%, Al2O3For 0.38%, Fe2O3It is 0.53%；
The crystal water of gypsum of slurry D: 15.08%.
αsemiwatergypsum product: the crystallization water 5.66%, total P2O5For 0.07%, water-soluble P2O5It is for 0.02%, total F
0.10%, water-soluble F is 0.03%, and whiteness 47.2%, gypsum crystalline form is hexagonal prism body, and draw ratio has 1~3, and gypsum is physical
Mark thick 37% can be detected, it is 5 minutes pre-hardening, final set 8 minutes, 2 hours anti-folding 7.5MPa, over dry resistance to compression 49.8MPa.
Tradition is produced the thick semi-hydrated gypsum generated in half water process phosphoric acid by being recrystallized to give α high twice by this comparative example
Strong gypsum does not scrape the foam in reactor in the process, does not add hydrogen peroxide bleaching gypsum yet.Although finally obtained gypsum also can
Reach the standard of α high strength gypsum, but whiteness is significant lower, and black organic matter also affects the strong of gypsum to a certain extent
Degree, thus intensity is declined for the white gypsum in 1~embodiment of embodiment 3.
Claims (13)
1. the method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is characterised in that include the following steps:
(1) the mixed slurry B that half water phosphoric acid and semi-hydrated gypsum is made is reacted with phosphorus ore using mixture of sulfuric phosphoric acid；
(2) half water phosphoric acid product of high concentration and thick semi-hydrated gypsum C are obtained after mixed slurry B filtering；
(3) thick semi-hydrated gypsum C is converted to two water by recrystallizing reactive moieties under the conditions of a certain concentration mixture of sulfuric phosphoric acid and temperature
Gypsum obtains slurry D；
(4) slurry D continues recrystallization reaction generation α under conditions of mixture of sulfuric phosphoric acid concentration and temperature are above step (3)
Semi-hydrated gypsum obtains slurry E；
(5) slurry E is filtered, washed, dries to obtain alpha type high-strength gypsum.
2. the method that phosphorus ore according to claim 1 produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is characterised in that: step
Suddenly at 85~100 DEG C, the liquid-solid ratio of the mixed slurry B is controlled in 2-10 the control of (1) reaction temperature.
3. the method that phosphorus ore according to claim 1 or 2 produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is characterised in that:
Step (3) reaction temperature is controlled at 40~70 DEG C；P based on mass fraction in liquid nitration mixture contained by the slurry D2O5For 1%~
10%, SO4 2-Content is 1%~8%.
4. the method that described in any item phosphorus ores produce half water phosphoric acid coproduction alpha type high-strength gypsum according to claim 1~3, special
Sign is: step (4) reaction temperature is controlled at 80~100 DEG C；In liquid nitration mixture contained by the slurry E based on mass fraction
P2O5For 13%~30%, SO4 2-Content is 12%~25%.
5. the method that phosphorus ore according to any one of claims 1 to 4 produces half water phosphoric acid coproduction alpha type high-strength gypsum, special
Sign is: the crystal water content mass fraction of gypsum is 12%~18% in step (3) the slurry D.
6. the method that described in any item phosphorus ores produce half water phosphoric acid coproduction alpha type high-strength gypsum according to claim 1~5, special
Sign is to include the following steps:
(1) concentrated sulfuric acid, half water phosphoric acid of part, filtrate F, ground phosphate rock are added in reactor R1 and are reacted, control reaction temperature
It 85~100 DEG C, is stirred to react 2~8 hours, obtains slurry B；
(2) slurry B is squeezed into filter X1 filtering, isolates half water phosphoric acid and thick semi-hydrated gypsum C, half water phosphoric acid separates part and returns
It returns reactor R1 to be recycled, partially enters reactor R3 and use；
(3) thick semi-hydrated gypsum C, gypsum wash water H are added in reactor R2 and carry out recrystallization reaction, control reaction temperature 40~70
DEG C, it is stirred to react 1~4 hour, obtains slurry D；
(4) half water phosphoric acid of part, the concentrated sulfuric acid obtained by step (2), slurry D are added in reactor R3 and carry out recrystallization reaction, controlled
It 80~100 DEG C of reaction temperature processed, is stirred to react 1~6 hour, obtains slurry E；
(5) slurry E is squeezed into filter X2 filtering, isolates filtrate F and gypsum filter cake, gypsum filter cake is washed to obtain stone with hot water
Cream wash water H and gypsum wet feed G, filtrate F Returning reactor R1 are recycled, and gypsum wash water H Returning reactor R2 is recycled, will
Gypsum wet feed G is sent into dryer M1 drying, obtains the high-strength white gypsum of the higher α type of whiteness.
7. the method that phosphorus ore according to claim 6 produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is characterised in that: step
Suddenly (1) described concentrated sulfuric acid, half water phosphoric acid of part, filtrate F, ground phosphate rock 0.2~0.8:1 in mass ratio~2:2~10:1 are added anti-
It answers and is reacted in device R1.
8. the method that phosphorus ore according to claim 6 or 7 produces half water phosphoric acid coproduction alpha type high-strength gypsum, it is characterised in that:
Thick semi-hydrated gypsum C, gypsum wash water H 1:0.5 in mass ratio~3 are added in reactor R2 and carry out recrystallization reaction by step (3).
9. special according to the method that the described in any item phosphorus ores of claim 6~8 produce half water phosphoric acid coproduction alpha type high-strength gypsum
Sign is: half water phosphoric acid of step (4) part, the concentrated sulfuric acid, slurry D be in mass ratio 1~5:1~3:10 be added in reactor R3 into
Row recrystallization reaction.
10. the method that phosphorus ore according to claims 1 to 9 produces half water phosphoric acid coproduction alpha type high-strength gypsum, feature exist
In phosphorus ore Powder Particle Size < 0.5mm described in step (1), moisture < 15% based on mass fraction, butt burns based on mass fraction to be lost
Measure < 10%, SiO2< 12%, MgO < 3%, BPL > 65%.
11. the method that described in any item phosphorus ores produce half water phosphoric acid coproduction alpha type high-strength gypsum according to claim 1~10,
It is characterized in that: scraping grey black foam A in step (1) reaction process, until slurry surface without black foam, obtains mixed slurry
B。
12. the method that described in any item phosphorus ores produce half water phosphoric acid coproduction alpha type high-strength gypsum according to claim 1~11,
Be characterized in that: step (3) recrystallization process is added hydrogen peroxide and carries out decolorization.
13. the method that phosphorus ore according to claim 12 produces half water phosphoric acid coproduction alpha type high-strength gypsum, which is characterized in that
The hydrogen peroxide is the aqueous hydrogen peroxide solution that mass fraction containing hydrogen peroxide is 20~50%；Thick semi-hydrated gypsum C and hydrogen peroxide,
Gypsum wash water H 1:0.01~0.05:0.5 in mass ratio~3, which is added in reactor R2, to be reacted.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491974.7A CN110316708A (en) | 2019-06-06 | 2019-06-06 | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum |
| CN202010407929.1A CN111348632B (en) | 2019-06-06 | 2020-05-14 | Method for producing semi-hydrated phosphoric acid and co-producing alpha-type high-strength gypsum from phosphorite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910491974.7A CN110316708A (en) | 2019-06-06 | 2019-06-06 | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110316708A true CN110316708A (en) | 2019-10-11 |
Family
ID=68120287
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910491974.7A Pending CN110316708A (en) | 2019-06-06 | 2019-06-06 | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum |
| CN202010407929.1A Active CN111348632B (en) | 2019-06-06 | 2020-05-14 | Method for producing semi-hydrated phosphoric acid and co-producing alpha-type high-strength gypsum from phosphorite |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010407929.1A Active CN111348632B (en) | 2019-06-06 | 2020-05-14 | Method for producing semi-hydrated phosphoric acid and co-producing alpha-type high-strength gypsum from phosphorite |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN110316708A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902665A (en) * | 2019-12-12 | 2020-03-24 | 昆明川金诺化工股份有限公司 | Method for improving semi-hydrated phosphoric acid concentration and washing rate |
| CN111392702A (en) * | 2020-03-20 | 2020-07-10 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN112897490A (en) * | 2021-04-02 | 2021-06-04 | 中国五环工程有限公司 | Method for producing wet-process phosphoric acid by multi-recrystallization semi-water-dihydrate and semi-water-dihydrate wet-process phosphoric acid production system |
| CN113148968A (en) * | 2021-05-24 | 2021-07-23 | 云南云天化股份有限公司 | Method for producing alpha-semi-hydrated gypsum by wet-process phosphorus processing |
| CN115893885A (en) * | 2022-12-02 | 2023-04-04 | 湖北省生态环保有限公司 | Phosphogypsum immersion cleaning agent and phosphogypsum harmless treatment method |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112850674B (en) * | 2021-03-22 | 2022-10-11 | 云南磷化集团有限公司 | Production device and method for co-producing alpha-hemihydrate gypsum by two-step wet-process phosphoric acid |
| CN113120875B (en) * | 2021-04-25 | 2022-12-30 | 云南云天化股份有限公司 | Production method of low-impurity wet-process phosphoric acid and high-quality alpha-hemihydrate gypsum |
| CN114275803A (en) * | 2022-01-28 | 2022-04-05 | 贵州大学 | Method for deeply removing calcium and byproduct alpha high-strength gypsum from frozen acidolysis solution in nitrophosphate fertilizer process |
| CN115504695B (en) * | 2022-09-06 | 2023-12-12 | 宜昌邦普循环科技有限公司 | Phosphogypsum recycling method |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102001636B (en) * | 2010-09-26 | 2012-07-25 | 四川大学 | Method for producing broad-concentration phosphoric acid and clean plaster by middle-low grade phosphorus ore wet process |
| CN102718200B (en) * | 2012-07-10 | 2014-07-23 | 中海石油化学股份有限公司 | Method for preparing industrial-grade phosphoric acid by decomposing mid-low-grade phosphorite with nitric acid |
| CN105133003B (en) * | 2015-09-18 | 2018-02-06 | 金正大诺泰尔化学有限公司 | A kind of production method of phosphoric acid by wet process by-product αsemiwatergypsum whisker |
| CN105384157A (en) * | 2015-11-09 | 2016-03-09 | 东华工程科技股份有限公司 | Technology for producing phosphoric acid through half-hydrate-dihydrate method |
| CN106348266B (en) * | 2016-08-25 | 2019-02-12 | 贵州川恒化工股份有限公司 | The method that hemihydrate technique prepares phosphoric acid coproduction land plaster |
| CN106866009B (en) * | 2017-03-15 | 2019-04-12 | 贵州大学 | A kind of method that half water ardealite prepares alpha type high-strength gypsum |
| CN109292744B (en) * | 2018-09-04 | 2020-03-17 | 安徽六国化工股份有限公司 | Method for producing wet-process phosphoric acid and α semi-hydrated phosphogypsum from medium-grade phosphate ore |
-
2019
- 2019-06-06 CN CN201910491974.7A patent/CN110316708A/en active Pending
-
2020
- 2020-05-14 CN CN202010407929.1A patent/CN111348632B/en active Active
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110902665A (en) * | 2019-12-12 | 2020-03-24 | 昆明川金诺化工股份有限公司 | Method for improving semi-hydrated phosphoric acid concentration and washing rate |
| CN110902665B (en) * | 2019-12-12 | 2022-11-15 | 昆明川金诺化工股份有限公司 | Method for improving semi-hydrated phosphoric acid concentration and washing rate |
| CN111392702A (en) * | 2020-03-20 | 2020-07-10 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN111392702B (en) * | 2020-03-20 | 2021-11-26 | 贵州川恒化工股份有限公司 | Method for preparing concentrated phosphoric acid and gypsum powder by semi-hydrated dihydrate process |
| CN112897490A (en) * | 2021-04-02 | 2021-06-04 | 中国五环工程有限公司 | Method for producing wet-process phosphoric acid by multi-recrystallization semi-water-dihydrate and semi-water-dihydrate wet-process phosphoric acid production system |
| CN113148968A (en) * | 2021-05-24 | 2021-07-23 | 云南云天化股份有限公司 | Method for producing alpha-semi-hydrated gypsum by wet-process phosphorus processing |
| CN115893885A (en) * | 2022-12-02 | 2023-04-04 | 湖北省生态环保有限公司 | Phosphogypsum immersion cleaning agent and phosphogypsum harmless treatment method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111348632B (en) | 2021-12-03 |
| CN111348632A (en) | 2020-06-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110316708A (en) | The method that phosphorus ore produces half water phosphoric acid coproduction alpha type high-strength gypsum | |
| RU2690358C1 (en) | Method for production of extraction phosphoric acid with obtained as by-product of alpha-hemihydrate gypsum and alpha-semi-aqueous gypsum with high degree of purity and high degree of whiteness | |
| WO2017045520A1 (en) | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process | |
| CN104005086B (en) | The method of Dihydrate gypsum whiskers prepared by a kind of ardealite | |
| CN109290060A (en) | A kind of process for subsequent treatment and phosphate ore floatation method of phosphate ore flotation tailings | |
| CN102925956B (en) | Method for preparing calcium sulfate hemihydrate whiskers by taking ardealite as main raw material | |
| CN106185853B (en) | The method for producing the high whiteness semi-hydrated gypsum of feed grade Wet Phosphoric Acid Market co-producing high-purity | |
| CN101555033B (en) | Method for preparing cryolite and coproducing soluble glass by using hydrof luorosilicic acid | |
| CN104649286B (en) | A kind of method that kodalk and sodium perborate are produced from boron concentrate | |
| CN104928758B (en) | A kind of additive package and method for producing anhydrous dead roasting type calcium sulfate crystal whiskers | |
| CN105154979A (en) | Method for producing wet-process phosphoric acid and coproducing alpha-semi-hydrated gypsum whisker and high-purity high-whiteness alpha-semi-hydrated gypsum whisker | |
| CN107419335A (en) | The method that hydrochloric acid method Cycle-decomposition ardealite and phosphorus mine tailing prepare calcium sulfate crystal whiskers | |
| CN105692668B (en) | A kind of gangue, coal ash for manufacturing for cryolite with high molecular ratio method | |
| CN103979584A (en) | Process for preparing light magnesium carbonate from boron mud | |
| CN110422830A (en) | The method for preparing calcium monohydrogen phosphate and ammonium chloride using flotation phosphate tailing | |
| CN106145164A (en) | The method preparing lithium carbonate from lepidolite | |
| CN105236778A (en) | Production method of wet phosphoric acid byproducts comprising highly pure and highly white alpha-semi-hydrated gypsum and inorganic-organic compound fertilizer | |
| CN105350066B (en) | A kind of method that ardealite prepares hemihydrate calcium sulfate crystal whisker | |
| CN1994880A (en) | Process for preparing white carbon black using attapulgite clay | |
| CN101830475A (en) | Method for preparing magnesium silicate and magnesium hydroxide from serpentine or tailings thereof | |
| US3055733A (en) | Upgrading alkali metal silicofluoride | |
| CN106745124A (en) | A kind of technique that aluminium hydroxide and concrete admixture are produced from Coaseries kaolin | |
| CN110407219A (en) | A kind of preparation process improving kaolin whiteness | |
| CN105110353A (en) | Method for carbonizing by-product soda solution used for water treatment by using micro-silicon powder as raw material | |
| CN108726525A (en) | A kind of method of lateritic nickel ore leached mud production waterglass |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191011 |