CN107840317B - A kind of-half water wet method phosphoric acid manufacture process of two water of one-step method - Google Patents
A kind of-half water wet method phosphoric acid manufacture process of two water of one-step method Download PDFInfo
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- CN107840317B CN107840317B CN201711032797.3A CN201711032797A CN107840317B CN 107840317 B CN107840317 B CN 107840317B CN 201711032797 A CN201711032797 A CN 201711032797A CN 107840317 B CN107840317 B CN 107840317B
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- 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
- C01B25/231—Dihydrate-hemihydrate process
Abstract
The present invention relates to a kind of-half water wet method phosphoric acid manufacture process of two water of one-step method.The invention includes the following steps: leaching reacts ,-half water conversion of two water, growing the grain, separates, is filtered, washed, passes through and control each process index acquisition high concentration finished product phosphoric acid filter liquor and high-quality by-product ardealite.P in the finished product phosphoric acid filter liquor that the present invention produces2O5Concentration about 35%, can avoid Phosphoric Acid Concentration investment, and energy-saving effect is good；In addition phosphorus conversion ratio, Washing ratio are high, the final total P of by-product ardealite2O5Content≤0.5%, water-soluble P2O5Content≤0.15%, P2O5Yield reaches 98%.The present invention maintains the characteristics of traditional two water of two step method-hemihydrate technique energy-saving effect is good, phosphrus reagent is high, by-product high-quality alpha-semi water plaster stone, two water filter progress are eliminated simultaneously, shorten process flow, device operating rate is improved, solves the problems, such as that filter cloth washing water is excessive and cannot achieve systematic water balance.
Description
Technical field
The invention belongs to phosphoric acid production technical fields, are specifically related to a kind of-half water Wet-process Phosphoric Acid Production of two water of one-step method
Technique.
Background technique
Phosphoric acid industry production method can be divided into thermal phosphoric acid and phosphoric acid by wet process two major classes.China is that phosphorous acid production by BEP is big
State, technical maturity, but since thermal phosphoric acid energy consumption is huge, environmental pollution is serious, P2O5Yield is low, is limited it by industrial policy
Production capacity is just gradually substituted by phosphoric acid by wet process.The phosphoric acid produced with the strong acid such as sulfuric acid, hydrochloric acid, nitric acid, fluosilicic acid decomposing phosphate rock
It is referred to as phosphoric acid by wet process.Wet-process Phosphoric Acid Production method (two water object CaSO usually in the form of crystal of calcium sulfate4·2H2O, half water object α-
CaSO4·1/2H2O and anhydride CaSO4) classify, successfully realize that the Wet Processes of Phosphoric Acid of industrial applications is main at present
Have: two water laws, Ban Shui-two water law ,-half water law of two water and half water object method.Wherein-two water law of half water can be divided into half water-two again
Water diluted acid method (one-step method) He Banshui-two water concentrated acid method (two step method)；- half water law of two water only has two step method process to have industry at present
Change application, there has been no document reports for one-step method process.
Table 1: the main feature of several phosphoric acid wet process techniques
There are the more defects such as energy consumption height, low, the ardealite comprehensive utilization difficulty of phosphrus reagent for traditional two water law phosphoric acid processes, but
The technique has the greater advantage adaptable to phosphorus ore, operating rate is high, is still used at present by the enterprise in 80% or more the world.
Chinese phosphorus ore reserves are big, but impurity content is high in phosphorus ore, belongs to mid low grade phosphate rock mostly, is restricted by phosphorus ore quality, therefore domestic
90% factory has selected two traditional water law phosphoric acid processes to carry out Wet-process Phosphoric Acid Production.
As national environmental protection dynamics continues to increase, energy-saving, environmental improvement and money increasingly fierce with industry competition
Source comprehensively utilizes increasingly by the great attention of enterprise, traditional phosphate dihydrate process energy consumption height, resource loss, ardealite ring
Huge obstacle of the problems such as border is polluted as Business survival and development.Country's phosphate dihydrate manufacturing enterprise's phosphoric acid concentration is 20 at present
~25%P2O5, reduced vapor consumption is greatly.The total P of the gypsum of phosphate dihydrate by-product2O5Content is 1% or so, not only brings phosphor resource
It is lost, while ardealite discharge and stockpiling process are also easy to produce a large amount of sour waters, to increase risk of environmental pollution, increase
Enterprise operation cost.Under normal circumstances, Wet-process Phosphoric Acid Production 1t P2O5By-product 5t or so ardealite is wanted, due to China's phosphate dihydrate
Technique ardealite impurity content is high, and comprehensive utilization is difficult, thereby results in ardealite and largely stacks.According to incompletely statistics, end
China's ardealite in 2016 adds up discharge amount up to 3.5 hundred million tons, and volume of cargo in storage is more than 2.5 hundred million tons, increases ardealite newly about every year at present
80000000 tons, to the end of the year 2016, China's ardealite comprehensive utilization ratio is less than 30%.
Energy-saving and emission-reduction are surrounded in recent years, and Wet-process Phosphoric Acid Production enterprise, China introduces or digests and assimilates in succession foreign technology, adopts
Wet-process Phosphoric Acid Production is carried out with two step method semiwater-diaquo phosphoric acid technique, the technique finished product phosphoric acid concentration is high, and phosphoric acid does not need dense
Contracting, energy-saving effect are significant；Gypsum quality is good, greatly reduces the environmental pollution of ardealite discharge, improves the comprehensive benefit of ardealite
With rate.But requirement of the semiwater-diaquo phosphoric acid technique to phosphorus ore is high, is only suitable for having enterprise's selection of high-quality phosphate rock resource to found the factory；With
This simultaneously, which requires stringent, requires equipment material high, production is difficult to keep long-period stable operation, causes
Cost of goods manufactured rises.In conclusion semiwater-diaquo phosphoric acid production technology does not have wide popularization and application still in China at present
Condition.
- half water phosphoric acid process (two step method) of two water is Belgian Pu Laiang house journal technology, which uses secondary counter
It answers, the recrystallization technology of secondary filter, its main feature is that 35%P can be produced2O5Left and right intermediate concentration phosphoric acid, have compared with
Good energy-saving effect；The phosphrus reagent of device production is high, while the good alpha-semi water plaster stone of by-product, ardealite comprehensive utilization value
It is high.But since the process flow is longer, plant investment increases, operating rate decline；Simultaneously as the process uses secondary filter,
Filter cloth washing water quantity is big, is difficult to solve that (Pu Laiang company is carried out using ground phosphate rock with phosphate ore pulp production system water balance
Production), the technique is still in the research and development stage at home at present.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of-half water wet method phosphoric acid manufacture process of two water of one-step method, should
Technique has the characteristics that reduce energy consumption, improve reclamation of phosphorus resource rate and obtain high-quality by-product ardealite.
In order to achieve the object of the present invention, the invention adopts the following technical scheme:
A kind of-half water wet method phosphoric acid manufacture process of two water of one-step method, comprising the following steps:
S1, leaching reaction: phosphate ore pulp, 98% concentrated sulfuric acid and ardealite cleaning solution are sufficiently mixed and constitute reaction slurry simultaneously
It is stirred to react, 70~75 DEG C of reaction temperature of control leaching；
Contained phosphorus ore in the phosphate ore pulp, contained P in the ardealite cleaning solution2O5And the reaction slurry three matter
Amount is than being 1000:(770~829): (4704~5145)；The amount of 98% concentrated sulfuric acid put into the leaching reaction accounts in phosphorus ore
28~32wt% of theoretical amount needed for CaO and MgO reacts completely；
The leaching reaction reaches the index of equilibrium state are as follows: free sulfuric acid radical ion (SO4 2-) 10~20g/L of concentration, instead
Answer slurry volume solid content 24~26%, P in the filtrate of reaction slurry2O536~38wt% of concentration；
S2, conversion growing the grain: 98% concentrated sulfuric acid is continuously added in Xiang Suoshu reaction slurry, under the conditions of 100~104 DEG C first
Realize that dihydrate gypsum is crystallized to semi-hydrated gypsum crystallization conversion in reaction slurry, degree of supersaturation is simultaneously in successive elimination reaction slurry later
Form semi-hydrated gypsum crystallization；
The amount of 98% concentrated sulfuric acid put into the conversion growing the grain reaction accounts in phosphorus ore needed for CaO and MgO reacts completely
68~72wt% of theoretical amount；
The conversion growing the grain reaction reaches the index of equilibrium state are as follows: free sulfuric acid radical ion (SO4 2-) concentration 160~
180g/L, reaction slurry volume solid content 22~24%, P in the filtrate of reaction slurry2O534~36wt% of concentration；
S3, separate, be filtered, washed: by the reaction slurry by cyclone be formed hierarchically bottom slurry and on
The bottom slurry and upper slurry are carried out filters pressing respectively and obtain ardealite filter cake and finished product phosphoric acid filter liquor by layered material slurry；
The ardealite filter cake is washed with hot water, the water after washing, which is back to, to be constituted the ardealite in leaching reaction and wash
Wash liquid, P in the ardealite cleaning solution2O518~20wt% of concentration.
Further, the accounting that particle size is greater than 100 mesh in phosphorus ore in the step S1 is 75~100wt%.
Further, slurry gained ardealite filter cake after filtering is used containing 7~9wt%CaO the step S3 at the middle and upper levels
Limewash carry out sprinkling neutralization.
Further, ardealite hot water countercurrent washing three times in the step S3.
Further, the mass ratio of the concentrated sulfuric acid used is 3:7 in the concentrated sulfuric acid used and step S2 in the step S1.
The beneficial effects of the present invention are:
(1) P in the finished product phosphoric acid filter liquor that present invention production obtains2O5Concentration about 35%, avoids Phosphoric Acid Concentration from putting into, energy conservation
Effect is good；In addition phosphorus conversion ratio, Washing ratio are high, the final total P of by-product ardealite2O5Content≤0.5%, water-soluble P2O5Content≤
0.15%, P2O5Yield reaches 98%.
The present invention maintains that traditional two water of two step method-hemihydrate technique energy-saving effect is good, phosphrus reagent is high, high-quality α-half water of by-product
The characteristics of gypsum, while two water filter progress are eliminated, process flow is shortened, device operating rate is improved, solves filter cloth punching
Wash water is excessive and cannot achieve systematic water balance problem (country is all made of ore pulp production).
Present invention process distinguishing feature: it is adaptable to phosphorus ore, it can be produced using mid low grade phosphate rock, be suitble to
State's national conditions；Obtain 35%P2O5The finished product phosphoric acid of left and right intermediate concentration reduces Phosphoric Acid Concentration steam consumption, has preferable energy conservation
Effect；Pass through-half water recrystallization technique of two water, P2O5Conversion ratio and Washing ratio are high, reduce phosphor resource loss；After filtration washing
Ardealite impurity content is low, acid small, and ardealite storage yard pollution is small, and ardealite working process is at low cost, and it is comprehensive to improve ardealite
Utilization rate.
(2) phosphorus ore is crushed 75% above by 100 meshes, the phosphorus ore to guarantee the abundant of leaching reaction by the present invention
Decomposition reaction generates CaSO in leaching reaction process4·2H2O crystallization passes through offer after leaching reaction reaches equilibrium state
Enough heats of dilution and free sulfuric acid radical ion (SO4 2-) concentration, guarantee gypsum crystallization by CaSO4·2H2O is crystallized to CaSO4·
1/2H2O crystallization conversion, the P during crystal transformation between a large amount of gypsum crystallizations2O5It is discharged into phosphoric acid solution, while anti-in slurry
Incomplete phosphorus ore is answered further sufficiently to be reacted, P2O5Conversion ratio greatly improves, as crystallization conversion reaction reaches equilibrium-like
Degree of supersaturation is eliminated in state, the further growing the grain curing of reaction slurry, ultimately forms CaSO coarse, with good strainability4·
1/2H2O crystallizes semi-hydrated gypsum.
(3) cyclone bottom slurry of the present invention through filtering, hot water countercurrent washing three times, the ardealite content of organic matter
It is low, crystallization is neat coarse, gypsum quality is good, this half water ardealite of part is sent into interior dry gypsum library by belt, for ardealite
Comprehensive utilization, can be directly used for building materials raw material, remarkable in economical benefits.The cyclone upper slurry is washed through filtering, hot water adverse current
It washs three times, send neutralisation treatment device to carry out sprinkling neutralization with the limewash of CaO content 8% or so by belt and (neutralize lime
Dosage is only 1/10th of traditional two hydraulic arts), the ardealite that pH value is neutralized to 8~10 passes through Belt Conveying to open storage ground
Harmless treatment (pH value is 6~9 after stacking 2 days).
(4) generated ardealite cleaning solution is realized for recycling in production process without waste water in production process of the present invention
It generates, meets existing environmentally friendly production requirement, enterprise's production run cost and energy consumption decline to a great extent.
(5) present invention process is applied widely, is not only suitable for the high phosphorus ore of grade, the phosphorus ore for being also suitble to grade low.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Fig. 2 is equipment therefor schematic diagram of the present invention.
Fig. 3,4 crystallize enlarged drawing (× 300) for invention by-product semi-hydrated gypsum.
Attached meaning marked in the figure is as follows:
1- reactive tank 2- conversion tank 3- digestive shelf 4- shurry pump
5- low level flash chamber 6- tail gas absorber 7- cyclone the first filter of 8-
9- phosphoric acid pump A 10- back scrubbing wash liquid pump A 11- mono- wash pump A 12- bis- wash pump A
Liquid pump B is washed in the pump B 15- back scrubbing of 13- the second filter 14- phosphoric acid
16- mono- washes pump B 17- bis- and washes pump B
Specific embodiment
More specific detail is made to technical solution of the present invention below with reference to embodiment:
Embodiment 1
S1, leaching reaction:
The phosphorus ore of 1000 parts of milleds is configured to phosphate ore pulp (H2O 30%, P2O530.02%, CaO 43.62%, MgO
1.48%, fineness is 100 mesh >=75%), 240 part of 98% concentrated sulfuric acid and continuously mixed from filter progress ardealite cleaning solution
It is added in reactive tank and carries out leaching reaction, leach 70~75 DEG C of reaction temperature, 98% concentrated sulfuric acid additional amount is reasonable to discuss sulfuric acid total amount
30% (sulfuric acid total amount depends on CaO and MgO in phosphorus ore and reacts required Theoretical Mass completely, and in addition 562 parts of addition convert
Slot).
Contained phosphorus ore in the phosphate ore pulp, contained P in the ardealite cleaning solution2O5And the reaction slurry three matter
Amount is than being 1000:800:4925.
Phosphorus ore is in reactive tank CaSO4-H3PO4-H2SO4-H2Reaction generates CaSO in O quaternary system4·2H2O crystallization.Reaction
CaSO in slot4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technic index: free sulphur acid group (SO4 2-) concentration
16.5g/L；Slurry volume solid content 25%；P in filtrate phosphoric acid2O5Concentration 37wt%.
S2, conversion growing the grain:
98% concentrated sulfuric acid is added to conversion tank in the overflow of reactive tank slurry in conversion tank, 98% concentrated sulfuric acid additional amount
It is reasonable by the 70% of sulfuric acid total amount, conversion tank CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technique and refers to
Mark: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 171g/L；Volume solid content 23%；P in filtrate phosphoric acid2O5Concentration
35wt%.The addition of above-mentioned 98% concentrated sulfuric acid provides enough heats of dilution and free sulphur acid group (SO4 2-) concentration, guarantee gypsum
Crystallization is in conversion tank by CaSO4·2H2O is crystallized to CaSO4·1/2H2O crystallization conversion, a large amount of gypsum during crystal transformation
Intergranular P2O5It is discharged into phosphoric acid solution, while reacting incomplete phosphorus ore in two water reactive tanks and sufficiently being reacted, P2O5Turn
Rate greatly improves.
The overflow of conversion tank slurry is to digestive shelf growing the grain, digestive shelf CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction
Equilibrium state technic index: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 171g/L；Volume solid content 23%；Filter
P in liquid phosphoric acid2O5Concentration 35wt%.Slurry further cures in digestive shelf, eliminates degree of supersaturation, ultimately form it is coarse, have it is good
The CaSO of good strainability4·1/2H2O crystallizes semi-hydrated gypsum.
Sulfuric acid is implemented segmentation and is added by the present invention, i.e., a part is added when leaching reaction, and another part is in crystallization conversion
It is added when reaction, both can guarantee the complete reaction of phosphorus ore in this way, effectively control the sulfate radical (SO that dissociates in finished product phosphoric acid filter liquor4 2-)
Concentration, reduce the leaching heat of dilution of reaction process, reaction heat, mitigate the pressure of cooling system, at the same in turn ensure crystallization from
Two water are converted to heat needed for half water process.
S3, it separates, be filtered, washed:
The overflow of digestive shelf slurry is sent into half water slurry cyclone by shurry pump and carries out slurry classification, eddy flow to shurry pump
Device bottom slurry and upper slurry are divided into two ardealite filters (band filter) and are filtered and washed, and contain 35%
P2O5The phosphoric acid filter liquor of left and right is sent to finished product phosphoric acid medial launder as finished acid；Filter cake carries out countercurrent washing three times with 70 DEG C of hot water,
Cleaning solution (P2O5Concentration is 19.2wt%) reactive tank is returned as rephosphorization acid；Ardealite after countercurrent washing three times, always
P2O5Content≤0.5%, water-soluble P2O5Content≤0.15%.
Embodiment 2
S1, leaching reaction:
The phosphorus ore of 1000 parts of milleds is configured to phosphate ore pulp (H2O 30%, P2O530.02%, CaO 43.62%, MgO
1.48%, fineness is 100 mesh >=75%), 224 part of 98% concentrated sulfuric acid and continuously mixed from filter progress ardealite cleaning solution
It is added in reactive tank and carries out leaching reaction, leach 70~75 DEG C of reaction temperature, 98% concentrated sulfuric acid additional amount is reasonable to discuss sulfuric acid total amount
30% (sulfuric acid total amount depends on CaO and MgO in phosphorus ore and reacts required Theoretical Mass completely, and in addition 578 parts of addition convert
Slot).
Contained phosphorus ore in the phosphate ore pulp, contained P in the ardealite cleaning solution2O5And the reaction slurry three matter
Amount is than being 1000:770:4704.
Phosphorus ore is in reactive tank CaSO4-H3PO4-H2SO4-H2Reaction generates CaSO in O quaternary system4·2H2O crystallization.Reaction
CaSO in slot4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technic index: free sulphur acid group (SO4 2-) concentration
10.0g/L；Slurry volume solid content 24%；P in filtrate phosphoric acid2O5Concentration 36wt%.
S2, conversion growing the grain:
98% concentrated sulfuric acid is added to conversion tank in the overflow of reactive tank slurry in conversion tank, 98% concentrated sulfuric acid additional amount
It is reasonable by the 70% of sulfuric acid total amount, conversion tank CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technique and refers to
Mark: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 180g/L；Volume solid content 22%；P in filtrate phosphoric acid2O5Concentration
34wt%.The addition of above-mentioned 98% concentrated sulfuric acid provides enough heats of dilution and free sulphur acid group (SO4 2-) concentration, guarantee gypsum
Crystallization is in conversion tank by CaSO4·2H2O is crystallized to CaSO4·1/2H2O crystallization conversion, a large amount of gypsum during crystal transformation
Intergranular P2O5It is discharged into phosphoric acid solution, while reacting incomplete phosphorus ore in two water reactive tanks and sufficiently being reacted, P2O5Turn
Rate greatly improves.
The overflow of conversion tank slurry is to digestive shelf growing the grain, digestive shelf CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction
Equilibrium state technic index: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 180g/L；Volume solid content 22%；Filter
P in liquid phosphoric acid2O5Concentration 34wt%.Slurry further cures in digestive shelf, eliminates degree of supersaturation, ultimately form it is coarse, have it is good
The CaSO of good strainability4·1/2H2O crystallization.
Sulfuric acid is implemented segmentation and is added by the present invention, i.e., a part is added when leaching reaction, and another part is in crystallization conversion
It is added when reaction, both can guarantee the complete reaction of phosphorus ore in this way, effectively control the sulfate radical (SO that dissociates in finished product phosphoric acid filter liquor4 2-)
Concentration, reduce the leaching heat of dilution of reaction process, reaction heat, mitigate the pressure of cooling system, at the same in turn ensure crystallization from
Two water are converted to heat needed for half water process.
S3, it separates, be filtered, washed:
The overflow of digestive shelf slurry is sent into half water slurry cyclone by shurry pump and carries out slurry classification, eddy flow to shurry pump
Device bottom slurry and upper slurry are divided into two ardealite filters (band filter) and are filtered and washed, and contain 34%
P2O5The phosphoric acid filter liquor of left and right is sent to finished product phosphoric acid medial launder as finished acid；Filter cake carries out countercurrent washing three times with 70 DEG C of hot water,
Cleaning solution (P2O5Concentration is 18.1wt%) reactive tank is returned as rephosphorization acid；Ardealite after countercurrent washing three times, always
P2O5Content≤0.5%, water-soluble P2O5Content≤0.15%.
Embodiment 3
S1, leaching reaction:
The phosphorus ore of 1000 parts of milleds is configured to phosphate ore pulp (H2O 30%, P2O530.02%, CaO 43.62%, MgO
1.48%, fineness is 100 mesh >=75%), 256 part of 98% concentrated sulfuric acid and continuously mixed from filter progress ardealite cleaning solution
It is added in reactive tank and carries out leaching reaction, leach 70~75 DEG C of reaction temperature, 98% concentrated sulfuric acid additional amount is reasonable to discuss sulfuric acid total amount
30% (sulfuric acid total amount depends on CaO and MgO in phosphorus ore and reacts required Theoretical Mass completely, and in addition 540 parts of addition convert
Slot).
Contained phosphorus ore in the phosphate ore pulp, contained P in the ardealite cleaning solution2O5And the reaction slurry three matter
Amount is than being 1000:829:5145.
Phosphorus ore is in reactive tank CaSO4-H3PO4-H2SO4-H2Reaction generates CaSO in O quaternary system4·2H2O crystallization.Reaction
CaSO in slot4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technic index: free sulphur acid group (SO4 2-) concentration
20/L；Slurry volume solid content 26%；P in filtrate phosphoric acid2O5Concentration 38wt%.
S2, conversion growing the grain:
98% concentrated sulfuric acid is added to conversion tank in the overflow of reactive tank slurry in conversion tank, 98% concentrated sulfuric acid additional amount
It is reasonable by the 70% of sulfuric acid total amount, conversion tank CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction equilibrium state technique and refers to
Mark: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 160g/L；Volume solid content 26%；P in filtrate phosphoric acid2O5Concentration
36wt%.The addition of above-mentioned 98% concentrated sulfuric acid provides enough heats of dilution and free sulphur acid group (SO4 2-) concentration, guarantee gypsum
Crystallization is in conversion tank by CaSO4·2H2O is crystallized to CaSO4·1/2H2O crystallization conversion, a large amount of gypsum during crystal transformation
Intergranular P2O5It is discharged into phosphoric acid solution, while reacting incomplete phosphorus ore in two water reactive tanks and sufficiently being reacted, P2O5Turn
Rate greatly improves.
The overflow of conversion tank slurry is to digestive shelf growing the grain, digestive shelf CaSO4-H3PO4-H2SO4-H2O quaternary system reaches reaction
Equilibrium state technic index: 100~104 DEG C of temperature；Free sulphur acid group (SO4 2-) concentration 160g/L；Volume solid content 26%；Filter
P in liquid phosphoric acid2O5Concentration 36wt%.Slurry further cures in digestive shelf, eliminates degree of supersaturation, ultimately form it is coarse, have it is good
The CaSO of good strainability4·1/2H2O crystallization.
Sulfuric acid is implemented segmentation and is added by the present invention, i.e., a part is added when leaching reaction, and another part is in crystallization conversion
It is added when reaction, both can guarantee the complete reaction of phosphorus ore in this way, effectively control the sulfate radical (SO that dissociates in finished product phosphoric acid filter liquor4 2-)
Concentration, reduce the leaching heat of dilution of reaction process, reaction heat, mitigate the pressure of cooling system, at the same in turn ensure crystallization from
Two water are converted to heat needed for half water process.
S3, it separates, be filtered, washed:
The overflow of digestive shelf slurry is sent into half water slurry cyclone by shurry pump and carries out slurry classification, eddy flow to shurry pump
Device bottom slurry and upper slurry are divided into two ardealite filters (band filter) and are filtered and washed, and contain 36%
P2O5The phosphoric acid filter liquor of left and right is sent to finished product phosphoric acid medial launder as finished acid；Filter cake carries out countercurrent washing three times with 70 DEG C of hot water,
Cleaning solution (P2O5Concentration is 20wt%) reactive tank is returned as rephosphorization acid；Ardealite after countercurrent washing three times, total P2O5
Content≤0.5%, water-soluble P2O5Content≤0.15%.
It is to be noted that the present invention is continuous production processes.
The following are the analysis indexes of finished product phosphoric acid filter liquor and ardealite that above-described embodiment produces:
Table 2 is finished product phosphoric acid filter liquor items analysis indexes:
Table 3 is that by-product ardealite analyzes indices:
By-product ardealite semihydrate crystal of the present invention is as shown in Figure 3,4.
Embodiment 4
By-product ardealite of the present invention is compared with traditional two hydraulic arts, and residual phosphorus, free F content are lower in ardealite, ardealite
It is acid small, it neutralizes consumption lime water and is greatly decreased, so that it is not up to standard to solve ardealite discharge in traditional phosphate dihydrate technique
Problem, while for ardealite comprehensive utilization create condition.Intuitively to reflect above-mentioned advantage, by the present invention and traditional two water
The pH value of the by-product ardealite of technique, free F content and acidity are detected and are compared, and are compared ardealite by test and are neutralized to
Consumed lime consumption when same pH value.
(1) ardealite pH value, free F, water solubility P2O5Content detection
The by-product ardealite of the present invention and traditional two hydraulic arts respectively takes 200g, and valve bag is installed, sealed.From above-mentioned self-styled
Four parts of samples are respectively weighed in bag, quality 10g is accurate to 0.02g, is placed in the drying conical flask of 250ml, and 200.00ml is added and goes
Ionized water is placed on magnetic stirring apparatus, and temperature is controlled at 25.0 DEG C ± 3.0 DEG C, stirs 30min, standing sedimentation 5min, with quick filter
Paper filtering, filtrate are collected in different dry glass containers, mark sealing.Filtrate 200mL is taken, the drying taper of 250ml is placed in
Bottle is added a certain amount of deionized water and is placed on magnetic stirring apparatus, and temperature is controlled at 25.0 DEG C ± 3.0 DEG C, and milk of lime is added dropwise, and is made entire
System pH to 5.0~8.0, standing sedimentation 5min successively record milk of lime consumption, are filtered with fast grade filter paper, and filtrate is collected
In the dry glass container of difference, identify, sealing.
Table 4 is the present invention and traditional two hydraulic art by-product ardealite pH values, free F, water solubility P2O5Content analysis:
The result shows that: by-product ardealite of the present invention can achieve " GB 5085-2007 hazardous waste judging standard ", and pass
Above-mentioned standard requirement is not achieved in two hydraulic art by-product ardealites of uniting.
(2) it is tested in ardealite with lime consumption
Configured milk of lime is titrated to the present invention and traditional two hydraulic art by-product ardealite filtrates, record consumption respectively
Amount.
Table 5 is to neutralize ardealite milk of lime consumption (milk of lime 0.65%)
By-product gypsum pH value of the present invention is neutralized to 5.0~8.0, lime 1~3.5mL/10g of breast amount, lime (100%CaO)
0.005~0.018g/10g of dosage；Same period Traditional Method process by-product ardealite pH value is neutralized to 5.0~8.0, and lime breast amount 15~
26mL/10g, 0.075~0.144g/10g of lime (100%CaO) dosage.It is converted to quick lime quantity of goods produced dosage (CaO content
90%) are as follows: neutralization ardealite (quantity of goods produced) PH of the present invention per ton to 5.0~8.0 lime consumptions is 0.55~2kg/t；And it neutralizes
Two hydraulic art ardealite (quantity of goods produced) PH of Traditional Method per ton is 8.3~16kg/ to 5.0~8.0 lime consumptions (CaO content 90%)
t。
The above results show: the ardealite of by-product of the present invention, and pH value and free F content are significantly lower than " GB 5085-
2007 hazardous waste judging standards " in indication range, and two traditional water law phosphoric acid process by-product ardealites, F, pH value be not up to
To state compulsion discharge standard, could be discharged after needing lime neutralisation treatment.The ardealite that the present invention discharges is neutralized to lime
It is only neutralize traditional two hydraulic art ardealite dosages 7~13% that pH value 5~8, which needs lime,.
Claims (5)
1. a kind of-half water wet method phosphoric acid manufacture process of two water of one-step method, comprising the following steps:
S1, leaching reaction: phosphate ore pulp, 98% concentrated sulfuric acid and ardealite cleaning solution are continuously sufficiently mixed and constitute reaction slurry simultaneously
It is stirred to react, 70~75 DEG C of reaction temperature of control leaching；
Contained phosphorus ore in the phosphate ore pulp, contained P in the ardealite cleaning solution2O5And the reaction slurry three mass ratio
For 1000:(770~829): (4704~5145)；The amount of 98% concentrated sulfuric acid put into the leaching reaction accounts for CaO in phosphorus ore
And MgO reacts 28~32wt% of required theoretical amount completely；
The leaching reaction reaches the index of equilibrium state are as follows: free sulfuric acid 10~20g/L of ion concentration, reaction slurry volume
Solid content 24~26%, P in the filtrate of reaction slurry2O536~38wt% of concentration；
S2, conversion growing the grain: 98% concentrated sulfuric acid is continuously added in Xiang Suoshu reaction slurry, is realized first under the conditions of 100~104 DEG C
Dihydrate gypsum is crystallized to semi-hydrated gypsum crystallization conversion in reaction slurry, degree of supersaturation and is formed in successive elimination reaction slurry later
Semi-hydrated gypsum crystallization；
The amount of 98% concentrated sulfuric acid put into the conversion growing the grain reaction accounts for theoretical needed for CaO and MgO in phosphorus ore reacts completely
68~72wt% of amount；
The conversion growing the grain reaction reaches the index of equilibrium state are as follows: free sulfuric acid 160~180g/L of ion concentration, reaction material
Slurry accumulates solid content 22~24%, P in the filtrate of reaction slurry2O534~36wt% of concentration；
S3, it separates, be filtered, washed: the reaction slurry being carried out to be formed hierarchically bottom slurry and upper layer material by cyclone
The bottom slurry and upper slurry are carried out filters pressing respectively and obtain ardealite filter cake and finished product phosphoric acid filter liquor by slurry；By institute
It states ardealite filter cake to be washed with hot water, the water after washing, which is back in the leaching reaction, constitutes the ardealite washing
Liquid, P in the ardealite cleaning solution2O518~20wt% of concentration.
2.-half water wet method phosphoric acid manufacture process of two water of one-step method as described in claim 1, it is characterised in that: the step S1
It is 75~100wt% that particle size, which is greater than the accounting of 100 mesh, in middle phosphorus ore.
3.-half water wet method phosphoric acid manufacture process of two water of one-step method as described in claim 1, it is characterised in that: the step S3
Slurry gained ardealite filter cake after filtering uses the limewash containing 7~9wt%CaO to carry out sprinkling neutralization at the middle and upper levels.
4.-half water wet method phosphoric acid manufacture process of two water of one-step method as described in claim 1, it is characterised in that: the step S3
The hot water countercurrent washing three times of middle ardealite.
5.-half water wet method phosphoric acid manufacture process of two water of one-step method as described in claim 1, it is characterised in that: the step S1
In in the concentrated sulfuric acid used and step S2 the mass ratio of the concentrated sulfuric acid used be 3:7.
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| CN109020282B (en) * | 2018-09-04 | 2019-10-11 | 安徽六国化工股份有限公司 | The method that middle-low grade phosphate produces phosphoric acid by wet process and half water ardealite of α |
| 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 |
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| CN113148968B (en) * | 2021-05-24 | 2022-12-30 | 云南云天化股份有限公司 | Method for producing alpha-semi-hydrated gypsum by wet-process phosphorus processing |
| CN113443614A (en) * | 2021-07-14 | 2021-09-28 | 东华工程科技股份有限公司 | Method for converting calcium sulfate dihydrate into alpha-calcium sulfate hemihydrate in dihydrate-hemihydrate wet-process phosphoric acid leaching process |
| CN116768171A (en) * | 2023-06-28 | 2023-09-19 | 昆明川金诺化工股份有限公司 | Process for producing high-quality semi-aqueous wet-process phosphoric acid |
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