CN105819415B - A kind of production method for the full utilization of resources of phosphorus ore that hydrochloric acid produces calcium hydrogen phosphate fodder - Google Patents
A kind of production method for the full utilization of resources of phosphorus ore that hydrochloric acid produces calcium hydrogen phosphate fodder Download PDFInfo
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- CN105819415B CN105819415B CN201610201221.4A CN201610201221A CN105819415B CN 105819415 B CN105819415 B CN 105819415B CN 201610201221 A CN201610201221 A CN 201610201221A CN 105819415 B CN105819415 B CN 105819415B
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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
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
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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
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/328—Defluorination during or after the preparation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/16—Halides of ammonium
- C01C1/164—Ammonium chloride
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
Abstract
The production method of the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder is produced the invention discloses a kind of hydrochloric acid, this method decomposing phosphate rock by chlorhydric acid, the acid non-soluble substance in phosphorus ore is detached as silicon resource product, then the calcium-phosphorus ratio and calcium fluorine ratio of solution are adjusted, directly use ammonia neutralization-precipitation reaction, the accurate defluorinate in the form of calcium fluoride precipitate, and concentration and separation obtains fluorine resource product；Continue to use ammonia precipitation calcium hydrogen phosphate fodder, separation of phosphorus resource product, calcium constituent resource in phosphorus ore fully enters calcium hydrogen phosphate fodder product, it is not the calcium carbonate byproduct removed calcium chloride and specially need the carbonate deposition separation that ammonia is added, this method has accomplished that the hydrochloric acid of " take do less more, a mine is multi-purpose " produces the economic means of the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder；Reach and economized on resources, reduce raw materials for production cost, improved the resource utilization of phosphorus ore, has increased the economic benefit of the producer, and the not clean manufacturing purpose of waste.
Description
Technical field
The present invention relates to the production methods that hydrochloric acid produces calcium hydrogen phosphate fodder, and feed phosphoric acid hydrogen is produced more particularly to hydrochloric acid
The production method of the full utilization of resources of phosphorus ore of calcium.
Background technology
Existing hydrochloric acid produces the production method of calcium hydrogen phosphate fodder, is to obtain phosphoric acid and calcium chloride with decomposing phosphate rock by chlorhydric acid
Mixed solution, then use milk of lime or calcium carbonate as neutralizer carry out neutralization precipitation fluoride, detach fluorine impurity slag after, continue
Neutralization precipitation goes out calcium monohydrogen phosphate, is dried after Isolating chlorinated calcium solution and obtains product, calcium chloride is as by-product according to region city
Field processing sell discards.(A.I is based on silica for four big main resource phosphorus, calcium, fluorine and silicon in phosphorus ore as shown in table 1
Acid non-soluble substance), be only using phosphor resource therein as the product processed of needs, in addition three large resource calcium, fluorine and element silicon are several
It is to be discarded with the useless sub-quilt of processing.
The representative phosphorus ore composition of table 1 and content
| Ingredient | P2O5 | Fe2O3 | Al2O3 | CaO | MgO | CO2 | SO3 | F | A.I | H2O |
| Form % | 30.87 | 2.23 | 0.84 | 42.46 | 0.38 | 0.72 | 0.15 | 2.2 | 19.66 | 1.35 |
It is produced as calcium hydrogen phosphate fodder, shortcoming is to use inorganic acid (including hydrochloric acid or sulfuric acid) by the calcium in phosphorus ore
Resource is separated with the compound form of calcium chloride or calcium sulfate, then uses lime or calcium carbonate raw material as the product of calcium monohydrogen phosphate
Calcium constituent precipitates phosphorus, is not utilized the calcium constituent resource in phosphorus ore as the calcium constituent in product.Such as reaction equation (2) institute
Show, 1 molecule phosphate radical is needed to match 1 molecular calcium in 1 molecule calcium monohydrogen phosphate；In addition 1.66 calcium in the decomposition of phosphorus ore acid, such as react
Shown in formula (1), 1 molecule phosphoric acid hydrogen of production shares the calcium for removing 2.66 molecules, wherein as useless when 1.66 molecular calciums are processed production
Pair discards.
Ca5F(PO4)3+ 10HCl=3H3PO4+5CaCl2+HF (1)
H3PO4+Ca(OH)2=CaHPO4·2H2O↓ (2)
Inventor is in patent No. ZL90105831.9 (patent names：Feedstuff calcium hydrogen phosphate production by defluorination with gravity floatation)
In patent, the hydrogen ion in the mix acid liquor obtained using decomposing phosphate rock by chlorhydric acid can dissolve the phosphorus because of defluorinate co-precipitation loss, will
Because of the phosphate precipitated from solution when precipitation defluorination, the method in solution is returned after dissolving, successfully solves feed phosphorus
The low problem of sour hydrogen calcium production defluorinate phosphrus reagent, is to have the unique production of feedgrade phosphate technology of China, this invention today
Principle almost all is used by industry.Thereafter again in patent No. ZL94111776.6 (patent names：A kind of Production By Sulfuric Acid Process phosphoric acid
And the method for solution containing phosphate) and patent No. ZL94111777.4 (patent names：A method of producing phosphoric acid extraction with hydrochloric acid)
In invention Deng series, successfully solves carbonate consumption sulfuric acid in production feed phosphate raw material phosphorus ore or hydrochloric acid is high asks
Topic, while the part calcium constituent resource in phosphorus ore is also utilized, save the acid produced and used and calcium raw material.In the patent No.
ZL201310437466.3 (patent names：A kind of production method of gypsum production cement joint production sulfuric acid) and the patent No.
ZL201410069087.8 (patent names：The method of the low silicon ardealite of high silicon Phosphate Rock acid by-product) etc. in patents of invention
Calcium constituent in phosphorus ore and element silicon are directly or indirectly subjected to circular economy processing or recycling.But with hydrochloric acid point
In the method for solving phosphorus ore production calcium hydrogen phosphate fodder, the complete utilization method of each element resource in phosphorus ore is not almost had been reported that also；It is existing
Have production in phosphorus ore because of the chlorination Calcium treatment of calcium resource by-product and market outlet problem, it has also become environmental protection and economy produce bottle
Neck be equally calcium constituent in product is not to utilize phosphorus ore the ardealite generated as Production By Sulfuric Acid Process feed phosphate
In calcium resource reason.Since the production technology of ammonia alkali legal system soda ash is to remove sodium chloride original with the principle of calcium chloride by-product
Chlorine element in material generates the calcium chloride of a large amount of by-products also because market does not digest, is only capable of being discharged into sea, leads to hydrochloric acid legal system
Make the by-product calcium chloride of calcium hydrogen phosphate fodder also without market, calcium resource is also wasted.
For this purpose, Chinese patent " a kind of method of hydrochloric acid Fodder making calcium monohydrogen phosphate and by-product calcium carbonate and ammonium chloride " is (specially
Profit number：ZL991182286 it) proposes：(1) ground phosphate rock amount 2-4% sodium salts or sylvite are added when extracting reaction as defluorinating agent；
(2) it is separated by solid-liquid separation when with the cleanser of alkaline ammoniate composition to PH to 1.2-2.0；(3) during the scavenging solution detached is used
It is centrifuged after being neutralized with agent, filtration cakes torrefaction obtains product calcium hydrogen phosphate fodder；(4) filtrate centrifuged, after
In continuous neutralizer until pH value 6.5-7.5, then the carbonate of ammonium is being added or is being passed through CO2, make the calcium chloride in solution
It is totally converted and is precipitated as CaCO3, then centrifuge, filtration cakes torrefaction obtains calcium carbonate byproduct；(5) the centrifugation filter of separation calcium carbonate
Liquid, by concentrating, cooling down obtained ammonium chloride by-product.
The purpose of the inventive method is nothing more than two：First using sodium potassium as defluorinating agent, with prodan or potassium
The fluoride that precipitation form precipitation abjection is brought by phosphorus ore, is made qualified calcium hydrogen phosphate fodder product；Second is to use ammonia
Carbonate or carbon dioxide precipitates go out the form of calcium carbonate byproduct and remove because of calcium extra in phosphorus ore.Its existing deficiency
Place is summarized as follows：
When using sodium or sylvite as defluorinating agent, and the 2-4% of phosphorus ore dosage is accounted for, equivalent ton product needs 50-70 public
Jin, increases the dosage and expense of adjuvant.
Second is that after using sodium or sylvite, the combination precipitating reagent of ammonia compound is still used, and still by the pH of solution
Value mentions 1.2-2.0, increases the production cost of defluorinate.
Third, the sodium or sylvite at least considerable part that use stay in last byproduct ammonium chloride, product matter is influenced
Amount.
Fourth, the filtrate of separation calcium hydrogen phosphate fodder, to remove excessive calcium in filtrate, then is neutralized to neutralizer
After pH value 6.5-7.5, the carbonate of ammonia is added or is passed through carbon dioxide precipitates Chlorine in Solution calcium at calcium carbonate and ammonium chloride, no
The carbonate or carbon dioxide raw material of ammonia are only needed, and the filtering of calcium carbonate and the ammonium chloride of washing filter cake liquid holdup are not only numb
Tired, also efficiency is low, and wash water is difficult to balance, and the quality of calcium carbonate is low, and value is low.
Fifth, the ammonium chloride mother liquor after separation calcium carbonate, because ammonium chloride belongs to strong acid weak base salt, ammonium chloride solution pH value is
4.2-5.6, or therefore with hydrochloric acid by the pH value of mother liquor by 7.5 recall to 4.2 or in concentration and evaporation free ammonia part with
Waste of steam is fallen.
Sixth, production technology is tediously long, a major product calcium hydrogen phosphate fodder, defluorination residues, calcium carbonate and ammonium chloride three are produced
Byproduct is separated by solid-liquid separation often, and production management is complicated and difficult.
Seventh, the silicon in phosphorus ore is mixed with defluorination residues and is separated off, its silicon is made to be difficult to the utilization of resources with fluorine.
So the production method that existing hydrochloric acid produces calcium hydrogen phosphate fodder almost rests on phosphor resource single in phosphorus ore
Utilize, i.e., on the phosphrus reagent of defluorination process, without by calcium constituent, fluorine element and the element silicon in phosphorus ore from atom economy
Angle carries out Commercial cultivation.Along with past hydrochloric acid method calcium hydrogen phosphate fodder need to salt acid starting material majority derive from organic chloride
Chemical product by-product, such as methanation chloromethanes, monoxone etc., because the progress of technology these productions are in circular economy technology
Under promotion, produced almost without by-product hydrochloric acid；And by-product hydrochloric acid production almost concentrates on production potassium sulfate or sulfenyl nitrogen-phosphorus-potassium is multiple
Hefei field produces the full utilization of resources of calcium hydrogen phosphate fodder for hydrochloric acid and provides better condition.
Invention content
In order to overcome above-mentioned hydrochloric acid to produce the shortcoming of calcium hydrogen phosphate fodder, by the calcium hydrogen phosphate fodder of sustainable development
Manufacturing requirements, take into account the full utilization of resources of phosphorus ore, the purpose of the present invention is that providing a kind of hydrochloric acid produces feed phosphorus
The method of the full utilization of resources of phosphorus ore of sour hydrogen calcium, the technical solution adopted is that：
A kind of production method for the full utilization of resources of phosphorus ore that hydrochloric acid produces calcium hydrogen phosphate fodder, includes the following steps successively：
A, phosphorus ore react the solution for generating phosphoric acid, calcium chloride and hydrofluoric acid with hydrochloric acid, then detach acid non-soluble substance；
B detaches the phosphoric acid and calcium chloride solution of the hydrofluoric acid containing after acid non-soluble substance, is passed through ammonia and carries out fluorine precipitation, generates
The phosphoric acid solution of calcium fluoride precipitate and ammonium chloride, is separated by solid-liquid separation；
C detaches the phosphoric acid and calcium chloride solution of calcium fluoride precipitate, continues to be passed through the precipitation that ammonia carries out phosphorus, generates feed
Calcium monohydrogen phosphate precipitates and the solution of ammonium chloride, is then separated by solid-liquid separation.
This method decomposing phosphate rock by chlorhydric acid detaches the siliceous resource of acid non-soluble substance in phosphorus ore；It is not added with any defluorinating agent, uses phosphorus
Calcium precise precipitation defluorinate in the form of calcium fluoride precipitate in mine, and it is enriched with fluorine resource；Supplement phosphoric acid by wet process makes phosphorite stope liquid
In calcium chloride all as the calcium in calcium hydrogen phosphate fodder product；It is not the carbon removed calcium chloride and specially need that ammonia is added
The calcium carbonate byproduct of hydrochlorate precipitation separation.
Generating principle of the present invention：
Ca5F(PO4)3+ 10HCl=3H3PO4+5CaCl2+HF (1)
6HF+SiO2=H2SiF6+2H2O (2)
CaCl2+2HF+NH3=CaF2↓+2NH4Cl (3)
H2SiF6+3CaCl2+6NH3·H2O=3CaF2↓+SiO2·4H2O+6NH4Cl (4)
H3PO4+CaCl2+2NH3·H2O=CaHPO4·H2O↓+2NH4Cl (5)
Specifically：
In step A, the phosphorus ore in the form of fluor-apatite, which is reacted with hydrochloric acid by above-mentioned reaction equation (1), generates phosphoric acid, calcium chloride
With the solution of hydrofluoric acid；The acid non-soluble substance (A.I) of wherein most of silicon oxide-containings stays in the solution as solid, minimal amount of work
Property silica generate fluosilicic acid by reaction equation (2), acid non-soluble substance therein can utilize directly as construction material；
In step B, detach the phosphoric acid and calcium chloride solution of acid non-soluble substance hydrofluoric acid containing, be passed through ammonia by reaction equation (3) and
(4) precipitation for carrying out fluorine, generates the phosphoric acid solution of calcium fluoride precipitate and ammonium chloride, calcirm-fluoride is as the fluorine utilization of resources；
In step C, the phosphoric acid and calcium chloride solution of calcium fluoride precipitate are detached, continues to be passed through ammonia by reaction equation (5) progress
The precipitation of phosphorus generates the solution of calcium hydrogen phosphate fodder precipitation and ammonium chloride；The mother liquor of the separation calcium hydrogen phosphate fodder is through overrich
After contracting, production composite fertilizer is directly sent to, without cooling and Crystallization Separation again.
Wherein, acid non-soluble substance, that is, silicon compound in step A can be utilized directly as construction material；Fluorine in step B
Change calcium as the fluorine utilization of resources；For calcium monohydrogen phosphate in step C as feed product, ammonium chloride can be used as fertilizer product to utilize；
So that silicon, fluorine, phosphorus and calcium are all rationally utilized.
As preferred technical solution：In step B, before being passed through ammonia, the phosphoric acid by wet process produced by sulfuric acid is added, into
Calcium/phosphorus molar ratio and calcium/fluorine molar ratio adjustment in row solution.The phosphoric acid by wet process is the wet method of sulfuric acid decomposition phosphorus ore production
Phosphoric acid and other not calcic phosphoric acid.
As further preferred technical solution：In step B, before being passed through ammonia, it is additionally added in a part of step C and divides
The washing lotion of ammonium chloride solution or washing calcium hydrogen phosphate fodder precipitation after being precipitated from calcium hydrogen phosphate fodder, the ammonium chloride solution of return
Amount be added in order to control after solution in total phosphorus concentration with P2O5Meter is in 4%-7%P2O5, more preferably 5%-6%P2O5。
As technical solution still more preferably：The calcium/phosphorus molar ratio is 1, and calcium/fluorine molar ratio is 0.5.
As preferred technical solution：Phosphorus ore fineness described in step A is 10-100 mesh, preferably 20-40 mesh；The salt
Sour mass percentage concentration 5%-35%, preferably 15%-30%, hydrochloric acid dosage are the 103%-110% of theoretical decomposition amount.
As preferred technical solution：In step B, the pH value after ammonification is 0.8-1.6, preferably 1.0-1.4.
As preferred technical solution：In step C, the pH value after ammonification is 4.0-6.0, preferably 4.5-5.5.
As preferred technical solution：Step A, in B, C, before being separated by solid-liquid separation, sedimentation stiff is carried out in advance, water is used in combination
It is washed.
As a kind of preferably technical solution：
(1) decomposing phosphate rock by chlorhydric acid is used, the mixed liquor of the phosphoric acid and calcium chloride and acid non-soluble substance of hydrofluoric acid containing is obtained, is detached
The insoluble solid formation of acid wherein based on silica, and solid formation filter cake is washed；
(2) ammonium chloride mother liquor and the technique life of phosphoric acid by wet process and return is added in the mixed liquor after the insoluble solid formation of separating acid
Washing of Filter Cake liquid in production, adjust solution in phosphorus content in 45-60g/LP2O5Between, calcium phosphorus molar ratio Ca/P is 1, calcium fluorine mole
It is 0.5 than Ca/F；Neutralization-precipitation reaction directly is carried out with ammonia, it is≤1.6 to make solution pH value, and fluorine is precipitated in the form of calcirm-fluoride,
Reach the fluorine index request of best product quality, defluorinate liquid phosphorus fluorine ratio >=300, the solid fluorinated calcium of precipitation and separation enrichment, and
Solid fluorinated calcium filter cake is washed；
(3) filtrate of separation calcirm-fluoride is directly neutralized with ammonia again arrives solution pH value >=5.0, is settled out calcium hydrogen phosphate fodder,
It is separated by solid-liquid separation, filtration cakes torrefaction obtains product calcium hydrogen phosphate fodder, and is washed to filter cake；
(4) filtrate for isolating calcium monohydrogen phosphate is ammonium chloride solution, and part returns to precipitation calcirm-fluoride process adjustment control phosphorus
Acid concentration, most of by concentration, production of compound fertilizer is sold or is used in crystallization as product.
Compared with prior art, the principle of the present invention and advantageous effect：
The present invention is due to by main resource element phosphor, calcium, fluorine, the silicon contained in phosphorus ore, with hydrochloric acid Fodder making phosphorus
In the production of sour hydrogen calcium product, concentration and separation is utilized with classification respectively, has accomplished the atom economy benefit of phosphorus ore, no
The consumption of raw materials in calcium hydrogen phosphate fodder production is only reduced, and expands the wholly-owned source utilization rate of phosphorus ore；Work is shortened again
Skill flow, simplifies production equipment, reduces plant investment；Reach and saved the energy, reduced cost of material, has increased production
The production purpose of the economic benefit of person and the full utilization of resources of circular economy discharged without useless pair.The technology of the present invention shortens technique
Flow simplifies production equipment, reduces plant investment；Reach and saved the energy, reduced raw materials for production cost, has improved production
Ability reduces investment, increases the economic benefit of the producer, not the clean manufacturing purpose of waste.
Description of the drawings
Fig. 1 is the flow diagram for the full utilization of resources of phosphorus ore that hydrochloric acid of the present invention produces calcium hydrogen phosphate fodder.
Specific implementation mode
The present invention will be further described with reference to the accompanying drawings.
Percentage concentration described in following example each means mass percentage concentration unless stated otherwise.
Embodiment 1
As shown in Figure 1：By by crushing be milled down to the ground phosphate rock 7000kg/h (composition is shown in Table 1) of 20-40 mesh with it is a concentration of
The hydrochloric acid 15000kg/h of 25%HCl is added to acidolysis slot, carries out the acidolysis reaction of phosphorus ore, the reaction time after forty minutes, by acidolysis
Slurry is sent into subsider and is settled, and the lower part underflow material after sedimentation enters filter press and detached, filter cake 800kg/h works
Skill water is washed, and the silicon compound product of 2200kg/h aqueous 40% is obtained, and construction material mixed mud generation is used for as sand
It is used for sand material.
It is heavy that the filtrate and cleaning solution detached from silicon compound filter press is sent into fluorine after merging with the top supernatant liquid of subsider
In the slot of shallow lake, mixed liquor total amount 20600kg/h, be added 6080kg/h gas washing in SA production phosphoric acid by wet process (composition is shown in Table 2) and return
Filtrate 27400kg/h, the washing lotion 4600kg/h of centrifuge separation calcium hydrogen phosphate fodder and calcium hydrogen phosphate fodder subsider top are clear
Solution is configured to phosphorus content 5.0%P by liquid 10940kg/h2O5Concentration, calcium phosphorus molecular proportion Ca/P are 1, and calcium fluorine molecule ratio Ca/F is
0.5；It is passed through ammonia and carries out neutralization reaction precipitation calcirm-fluoride, when solution pH value reaches 0.8, stopping is passed through ammonia, continues to stir
After 15 minutes, the slurry for precipitating calcirm-fluoride feeding subsider is settled, while a small amount of flocculant is added；Lower part after sedimentation
Underflow material enters filter press and is detached, and filter cake is washed with 600kg/h process waters, obtains 1020kg/h's aqueous 52%
Fluorine compounds product, it is 37.6%F to calculate fluorine content with butt, for replacing fluorite (CaF2) former as Fluorine contained chemicals production
Material.
The filtrate and washing lotion detached from fluoride filter press is sent into calcium hydrogen phosphate fodder after merging with subsider upper clear supernate
Process is precipitated, merging mixed liquor total amount is 69200kg/h (main composition is shown in Table 3), is passed through ammonia progress neutralization reaction precipitation and raises
Expect calcium monohydrogen phosphate, when solution pH value reaches 5.0, stopping is passed through ammonia, continues stirring after twenty minutes, will precipitate feed phosphoric acid hydrogen
The slurry of calcium is sent into subsider and is settled；Lower part underflow material after sedimentation enters centrifuge and is detached, and filter cake is used
6300kg/h process waters are washed, and the calcium hydrogen phosphate fodder product of 8000kg/h aqueous 21% is obtained, and calculating phosphorus with butt contains
Amount is 18.06%P, fluorine content 0.11%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 95.8%.
Filtrate 27400kg/h, the washing lotion 4600kg/h and calcium hydrogen phosphate fodder subsider upper clear supernate detached from centrifuge
10940kg/h returns to fluorine precipitation tank in phosphoric acid solution after dilution separation silicon compound, adding up to；It is heavy from calcium hydrogen phosphate fodder
Upper clear supernate 24960kg/h (the containing ammonium chloride 22.04%NH of slot drop4Cl it) is sent into evaporation concentrator and is evaporated concentration production chlorine
Change ammonium product or is used as production of compound fertilizer raw material, the ammonium chloride product 5500kg/h in terms of butt.
2 phosphoric acid by wet process of table forms and content
| Composition | P2O5 | F | CaO | Fe2O3 | Al2O3 | MgO | SO3 | P/F |
| Content (%) | 23.21 | 1.70 | 0.22 | 0.53 | 0.48 | 0.42 | 1.84 | 5.90 |
3 phosphoric acid defluorination of table mainly forms
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 4.98 | 0.013 | 7.82 | 14.50 | 167 |
Embodiment 2
As shown in Figure 1：By by crushing be milled down to the ground phosphate rock 7000kg/h (composition is shown in Table 4) of 20-40 mesh with it is a concentration of
The hydrochloric acid 22750kg/h of 21%HCl is added to acidolysis slot, carries out the acidolysis reaction of phosphorus ore, the reaction time after forty minutes, by acidolysis
Slurry is sent into subsider and is settled, and the lower part underflow after sedimentation enters filter press and detached, filter cake 400kg/h process waters
It is washed, obtains the silicon compound product of 750kg/h aqueous 60%, mortar is replaced for construction material mixed mud as sand
It uses.
It is heavy that the filtrate and cleaning solution detached from silicon compound filter press is sent into fluorine after merging with the top supernatant liquid of subsider
Shallow lake slot merges mixed liquor total amount 29400kg/h, and the phosphoric acid by wet process (composition is shown in Table 5) of 11366kg/h gas washing in SA production is added and returns
Centrifuge separation calcium hydrogen phosphate fodder filtrate 26833kg/h, washing lotion 7365kg/h and calcium hydrogen phosphate fodder subsider top
Solution is configured to phosphorus content 5.50%P by clear liquid 4072kg/h2O5Concentration, calcium phosphorus molecular proportion Ca/P are 1, calcium fluorine molecule ratio Ca/F
It is 0.5；It is passed through ammonia and carries out neutralization reaction precipitation calcirm-fluoride, when solution pH value reaches 1.0, stopping is passed through ammonia, continues to stir
After mixing 15 minutes, the slurry for precipitating calcirm-fluoride feeding subsider is settled, while a small amount of flocculant is added；Under after sedimentation
Portion's underflow enters filter press and is detached, and filter cake is washed with 900kg/h process waters, obtains the fluorine of 2284kg/h aqueous 60%
Compound products, it is 40.2%F to calculate fluorine content with butt, for replacing fluorite (CaF2) former as Fluorine contained chemicals production
Material.
Total amount 77646kg/h is (main after the filtrate and washing lotion detached from fluoride filter press merges with subsider upper clear supernate
It forms to be shown in Table and 6) is sent into calcium hydrogen phosphate fodder precipitation process, be passed through ammonia and carry out neutralization reaction precipitation calcium hydrogen phosphate fodder, when
When solution pH value reaches 5.0, stopping is passed through ammonia, continues stirring after twenty minutes, and the slurry for precipitating calcium hydrogen phosphate fodder is sent into
Subsider is settled；Lower part underflow after sedimentation enters centrifuge and is detached, and filter cake is washed with 11000kg/h process waters
It washs, obtains the calcium hydrogen phosphate fodder product of 12774kg/h aqueous 18%, it is 17.06%P, fluorine content to calculate phosphorus content with butt
For 0.11%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 94.1%.
Filtrate 26770kg/h, the washing lotion 11500kg/h detached from centrifuge returns to fluorine precipitation tank for diluting separation silication
After conjunction object in phosphoric acid solution, add up to 38270kg/h；Upper clear supernate 38102kg/h (the containing ammonium chlorides of calcium hydrogen phosphate fodder subsider
24.49%NH4Cl evaporation concentrator) is sent into be evaporated concentration production ammonium chloride product or be used as production of compound fertilizer raw material, with
Butt meter ammonium chloride product 9329kg/h.
4 phosphorus ore of table forms and content
5 phosphoric acid by wet process of table forms and content
| Composition | P2O5 | F | CaO | Fe2O3 | Al2O3 | MgO | SO3 | P/F |
| Content (%) | 17.65 | 1.36 | 0.36 | 0.58 | 0.98 | 1.47 | 2.90 | 5.66 |
6 phosphoric acid defluorination of table mainly forms
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 5.35 | 0.016 | 8.77 | 12.01 | 145 |
Embodiment 3
As shown in Figure 1：By by crushing be milled down to the ground phosphate rock 7000kg/h (composition is shown in Table 7) of 20-40 mesh with it is a concentration of
The hydrochloric acid 17257kg/h of 27%HCl is added to acidolysis slot, carries out the acidolysis reaction of phosphorus ore, after 30 minutes reaction time, by acidolysis
Slurry is sent into subsider and is settled, and the lower part underflow after sedimentation enters filter press and detached, filter cake 500kg/h process waters
It is washed, obtains the silicon compound product of 1125kg/h aqueous 60%, sand is replaced for construction material mixed mud as sand
Slurry uses.
It is heavy that the filtrate and cleaning solution detached from silicon compound filter press is sent into fluorine after merging with the top supernatant liquid of subsider
Shallow lake slot merges mixed liquor total amount 23625kg/h, and the desulfurization that 15762kg/h presses patent No. ZL94111776.6 technique productions is added
Phosphoric acid by wet process (composition is shown in Table 8) detaches the filtrate 20743kg/h of calcium hydrogen phosphate fodder, washing lotion 11990kg/ with the centrifuge returned
Solution is configured to phosphorus content 6.00%P by h2O5Concentration, calcium phosphorus molecular proportion Ca/P are 1, and calcium fluorine molecule ratio Ca/F is 0.5；It is passed through ammonia
Gas carries out neutralization reaction and precipitates calcirm-fluoride, and when solution pH value reaches 1.4, stopping is passed through ammonia, will after continuing stirring 15 minutes
The slurry of precipitation calcirm-fluoride is sent into subsider and is settled, while a small amount of flocculant is added；Lower part underflow after sedimentation enters pressure
Filter is detached, and filter cake is washed with 1200kg/h process waters, obtains the fluorine compounds product of 3143kg/h aqueous 65%,
It is 31.82%F to calculate fluorine content with butt, for replacing fluorite (CaF2) it is used as Fluorine contained chemicals raw materials for production.
Total amount 70180kg/h is (main after the filtrate and washing lotion detached from fluoride filter press merges with subsider upper clear supernate
It forms to be shown in Table and 9) is sent into calcium hydrogen phosphate fodder precipitation process, be passed through ammonia and carry out neutralization reaction precipitation calcium hydrogen phosphate fodder, when
When solution pH value reaches 5.0, stopping is passed through ammonia, continues stirring after twenty minutes, and the slurry for precipitating calcium hydrogen phosphate fodder is sent into
Subsider is settled；Lower part underflow after sedimentation enters centrifuge and is detached, and filter cake is washed with 11000kg/h process waters
It washs, obtains the calcium hydrogen phosphate fodder product of 11974kg/h aqueous 18%, it is 17.90%P, fluorine content to calculate phosphorus content with butt
For 0.14%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 93.2%.
Filtrate 20743kg/h, the washing lotion 11990kg/h detached from centrifuge returns to fluorine precipitation tank for diluting separation silication
After conjunction object in phosphoric acid solution, add up to 38270kg/h；Upper clear supernate 30936kg/h (the containing ammonium chlorides of calcium hydrogen phosphate fodder subsider
22.08%NH4Cl evaporation concentrator) is sent into be evaporated concentration production ammonium chloride product or be used as production of compound fertilizer raw material, with
Butt meter ammonium chloride product 6830kg/h.
7 phosphorus ore of table forms and content
| Composition | P2O5 | Fe2O3 | Al2O3 | CaO | MgO | CO2 | SO3 | F | A.I | H2O |
| Content (%) | 28.16 | 2.28 | 1.54 | 45.0 | 1.63 | 3.89 | 0.05 | 3.10 | 7.47 | 1.06 |
8 phosphoric acid by wet process of table forms and content
| Composition | P2O5 | F | CaO | Fe2O3 | Al2O3 | MgO | SO3 | P/F |
| Content (%) | 14.95 | 1.12 | 1.64 | 0.26 | 1.10 | 0.20 | 0.31 | 5.80 |
9 phosphoric acid defluorination of table mainly forms
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 5.73 | 0.019 | 9.62 | 7.78 | 130 |
Claims (9)
1. a kind of hydrochloric acid produces the production method of the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder, which is characterized in that by following step
Rapid composition：
A, phosphorus ore react the solution for generating phosphoric acid, calcium chloride and hydrofluoric acid with hydrochloric acid, then detach acid non-soluble substance；
B, detach acid non-soluble substance after hydrofluoric acid containing phosphoric acid and calcium chloride solution, be added phosphoric acid by wet process, then pass to ammonia into
Row fluorine precipitates, and generates the phosphoric acid solution of calcium fluoride precipitate and ammonium chloride, is separated by solid-liquid separation；The phosphoric acid by wet process is by sulfuric acid point
The phosphoric acid by wet process produced by sulfuric acid is added before being passed through ammonia in the phosphoric acid by wet process that solution phosphorus ore is produced, and the calcium in progress solution/
Phosphorus molar ratio and calcium/fluorine molar ratio adjustment；
C detaches the phosphoric acid and calcium chloride solution of calcium fluoride precipitate, continues to be passed through the precipitation that ammonia carries out phosphorus, generates feed phosphoric acid
The solution of hydrogen calcium precipitate and ammonium chloride, is then separated by solid-liquid separation.
2. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 1 produces calcium hydrogen phosphate fodder,
It is characterized in that：In step B, before being passed through ammonia, it is additionally added in a part of step C after detaching calcium hydrogen phosphate fodder precipitation
The washing lotion of ammonium chloride solution or washing calcium hydrogen phosphate fodder precipitation.
3. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 2 produces calcium hydrogen phosphate fodder,
It is characterized in that：The calcium/phosphorus molar ratio is 1, and calcium/fluorine molar ratio is 0.5.
4. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 1 produces calcium hydrogen phosphate fodder,
It is characterized in that：Phosphorus ore fineness described in step A is 10-100 mesh；The hydrochloric acid mass percentage concentration 5%-35%, hydrochloric acid dosage
For the 103%-110% of theoretical decomposition amount.
5. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 1 produces calcium hydrogen phosphate fodder,
It is characterized in that：In step B, the pH value after ammonification is 0.8-1.6.
6. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 1 produces calcium hydrogen phosphate fodder,
It is characterized in that：In step C, the pH value after ammonification is 4.0-6.0.
7. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 1 produces calcium hydrogen phosphate fodder,
It is characterized in that：Step A, in B, C, before being separated by solid-liquid separation, sedimentation stiff is carried out in advance, water is used in combination to be washed.
8. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 4 produces calcium hydrogen phosphate fodder,
It is characterized in that：Phosphorus ore fineness described in step A is 20-40 mesh；The hydrochloric acid mass percentage concentration 15%-30%.
9. the production method for the full utilization of resources of phosphorus ore that a kind of hydrochloric acid according to claim 5 produces calcium hydrogen phosphate fodder,
It is characterized in that：In step B, the pH value after ammonification is 1.0-1.4.
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