CN105819415A - Phosphorus ore all-resource utilization production method preparing feed calcium hydrophosphate with hydrochloric acid - Google Patents
Phosphorus ore all-resource utilization production method preparing feed calcium hydrophosphate with hydrochloric acid Download PDFInfo
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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
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Abstract
The invention discloses a phosphorus ore all-resource utilization production method preparing feed calcium hydrophosphate with hydrochloric acid. According to the method, phosphorus ore is decomposed with hydrochloric acid, acid non-soluble substances in the phosphorus ore are used as a silicon resource product, the calcium-phosphorus ratio and the calcium-fluorine ratio of a solution are then adjusted, ammonia is directly used for neutralization and precipitation reactions, precise defluorination is realized in the form of calcium fluoride precipitation, and a fluorine resource product is obtained after enrichment and separation; ammonia is continuously used for precipitating feed calcium hydrophosphate, a phosphorus resource product is separated, a calcium resource in the phosphorus ore completely come into the feed calcium hydrophosphate product, and a calcium carbonate by-product which is subjected to precipitation separation performed by ammoniac carbonate is not specially required and added for removing calcium chloride. The method is an phosphorus ore all-resource utilization economic method which prepares feed calcium hydrophosphate with hydrochloric acid and realizes multiple purposes from one phosphorus ore and high productivity with few materials; resources are saved, the production raw material cost is lowered, the resource utilization ratio of the phosphorus ore is improved, the economic benefits of a producer are increased, and the cleaner production purpose of no waste is achieved.
Description
Technical field
The present invention relates to hydrochloric acid and produce the production method of calcium hydrogen phosphate fodder, particularly relate to the production method that hydrochloric acid produces the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder.
Background technology
Existing hydrochloric acid produces the production method of calcium hydrogen phosphate fodder, it it is the mixed solution obtaining phosphoric acid and calcium chloride with decomposing phosphate rock by chlorhydric acid, it is neutralized precipitating fluoride as nertralizer again with lime cream or calcium carbonate, after separating fluora matter slag, continue neutralization precipitation and go out calcium hydrogen phosphate, separated calcium chloride solution post-drying obtains product, and calcium chloride or discards according to regional markets processing sell as by-product.Four big Main Resources phosphorus, calcium, fluorine and silicon (A.I is the acid non-soluble substance based on silicon oxide) in phosphorus ore as shown in table 1, it is only that phosphor resource therein is almost discarded with the useless sub-quilt of processing as the product needing processing, other three large resource calcium, fluorine and element silicon.
Table 1 representative phosphorus ore composition and content
| Composition | P2O5 | Fe2O3 | Al2O3 | CaO | MgO | CO2 | SO3 | F | A.I | H2O |
| Composition % | 30.87 | 2.23 | 0.84 | 42.46 | 0.38 | 0.72 | 0.15 | 2.2 | 19.66 | 1.35 |
Produce as calcium hydrogen phosphate fodder, its weak point is the calcium resource in phosphorus ore to be separated with the compound form of calcium chloride or calcium sulfate with mineral acid (including hydrochloric acid or sulphuric acid), precipitate phosphorus with Calx or calcium carbonate raw material as the product calcium constituent of calcium hydrogen phosphate again, the calcium constituent resource in phosphorus ore is not utilized as the calcium constituent in product.As shown in reaction equation (2), 1 molecule calcium hydrogen phosphate need 1 molecular phosphorus acid group join 1 molecular calcium；1.66 calcium in decomposing plus phosphorus ore acid, as shown in reaction equation (1), produce 1 molecule phosphoric acid hydrogen and share the calcium of 2.66 molecules, wherein discard as useless pair during the processed production of 1.66 molecular calciums.
Ca5F(PO4)3+ 10HCl=3H3PO4+5CaCl2+HF(1)
H3PO4+Ca(OH)2=CaHPO4·2H2O↓(2)
Inventor is in the patent of patent No. ZL90105831.9 (patent name: feedstuff calcium hydrogen phosphate production by defluorination with gravity floatation), utilize the hydrion in the mix acid liquor that decomposing phosphate rock by chlorhydric acid obtains, can dissolve because of the phosphorus of defluorinate co-precipitation loss, by the phosphate because precipitating from solution during precipitation defluorination, the method in solution is returned after dissolving, successfully solve calcium hydrogen phosphate fodder and produce the problem that defluorinate phosphrus reagent is low, being to have the production of feedgrade phosphate technology that China is unique today, this inventive principle almost all is used by industry.The most again in the invention of the series such as patent No. ZL94111776.6 (patent name: a kind of Production By Sulfuric Acid Process phosphoric acid and the method for solution containing phosphate) and patent No. ZL94111777.4 (patent name: a kind of hydrochloric acid produces the method for phosphoric acid extraction), successfully solve and produce carbonate in feed phosphate raw material phosphorus ore and consume sulphuric acid or the high problem of hydrochloric acid, also utilize the part calcium constituent resource in phosphorus ore simultaneously, save acid and the calcium raw material of production and application.In the patents of invention such as patent No. ZL201310437466.3 (patent name: a kind of Gypsum Fibrosum produces the production method of cement joint production sulphuric acid) and patent No. ZL201410069087.8 (patent name: the method for the high silicon Phosphate Rock low silicon ardealite of acid by-product), the most directly or indirectly calcium constituent in phosphorus ore and element silicon are circulated economic processing or recycling.But, produce with decomposing phosphate rock by chlorhydric acid in the method for calcium hydrogen phosphate fodder, the most also do not have been reported that the complete utilization method of each element resource in phosphorus ore；Existing production in phosphorus ore because of calcium resource by-product calcium chloride process with market outlet problem, become the bottleneck that environmental protection and economy produces, as Production By Sulfuric Acid Process feed phosphate produce ardealite, be equally the calcium constituent in product be not the reason utilizing the calcium resource in phosphorus ore.Owing to the production technology of ammonia alkali legal system soda is the chlorine element removing in sodium chloride raw material by the principle of calcium chloride by-product, produce the calcium chloride of a large amount of by-product also because market does not digests, it is only capable of entering sea, causing the by-product calcium chloride of hydrochloric acid method Fodder making calcium hydrogen phosphate also without market, its calcium resource is also wasted.
To this end, Chinese patent " a kind of hydrochloric acid Fodder making calcium hydrogen phosphate and by-product calcium carbonate and the method for ammonium chloride " (patent No.: ZL991182286) proposes: (1) adds ground phosphate rock amount 2-4% sodium salt or potassium salt as defluorinating agent when extractive reaction；(2) with the cleanser of alkaline ammonia compound composition to carrying out solid-liquid separation during PH to 1.2-2.0；(3) the scavenging solution nertralizer separated carries out centrifugation after being neutralized, and filtration cakes torrefaction obtains product calcium hydrogen phosphate fodder；(4) filtrate of centrifugation, in continuation nertralizer to pH value 6.5-7.5, is then adding the carbonate of ammonium or is being passed through CO2, make the calcium chloride in solution be totally converted and be precipitated as CaCO3, then centrifugation, filtration cakes torrefaction obtains calcium carbonate side-product；(5) separate the centrifugal filtrate of calcium carbonate, prepare ammonium chloride by-product through concentrating, cooling down.
The purpose of this inventive method uses sodium potassium as defluorinating agent nothing more than two: first, precipitates, with the precipitation form of prodan or potassium, the fluoride that abjection brings because of phosphorus ore, prepares qualified calcium hydrogen phosphate fodder product；Second is that the form using the carbonate of ammonia or carbon dioxide precipitates to go out calcium carbonate side-product is removed because of calcium unnecessary in phosphorus ore.Its weak point existed is summarized as follows:
One is to use sodium or potassium salt as defluorinating agent, and accounts for the 2-4% of phosphorus ore consumption, and equivalent ton product needed 50-70 kilogram adds consumption and the expense of adjuvant.
After two are employing sodium or potassium salt, the combination precipitant of ammonia compound to be used, and be also intended to the pH value of solution is mentioned 1.2-2.0, add the production cost of defluorinate.
Three be use sodium or potassium salt at least considerable part stay in last side-product ammonium chloride, affect product quality.
Four is the filtrate separating calcium hydrogen phosphate fodder, for removing the calcium of excess in filtrate, it is neutralized to pH value 6.5-7.5 with nertralizer again, add the carbonate of ammonia or be passed through carbon dioxide precipitates Chlorine in Solution calcium and become calcium carbonate and ammonium chloride, not only needing carbonate or the carbon dioxide raw material of ammonia, and filtering of calcium carbonate not only bothers with the ammonium chloride washing filter cake liquid holdup, also efficiency is low, wash water is difficult to balance, and the quality of calcium carbonate is low, is worth low.
Five is the ammonium chloride mother liquor after separating calcium carbonate, and because ammonium chloride belongs to strong acid weak base salt, ammonium chloride solution pH value is 4.2-5.6, therefore or with hydrochloric acid by 7.5, the pH value of mother solution is recalled to 4.2, or the part of free ammonia is fallen with waste of steam when concentration and evaporation.
Six is that production technology is tediously long, produces a major product calcium hydrogen phosphate fodder, and defluorination residues, calcium carbonate and three side-products of ammonium chloride, often, production management is complicated and difficult for solid-liquid separation.
Seven is that the silicon in phosphorus ore mixes with defluorination residues and is separated off so that it is silicon and fluorine are difficult to the utilization of resources.
So, existing hydrochloric acid is produced the production method of calcium hydrogen phosphate fodder and is almost rested on phosphor resource utilization single in phosphorus ore, i.e. on the phosphrus reagent of defluorination process, and the calcium constituent in phosphorus ore, fluorine element and element silicon are not carried out Commercial cultivation from the angle of atom economy.Add over 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, monoxones etc., because these productions of progress of technology are under the promotion of recycling economy technology, produce almost without by-product hydrochloric acid；And by-product hydrochloric acid produces and almost concentrates on production potassium sulfate or sulfenyl nitrogen-phosphorus-potassium compound fertilizer field, produce the full utilization of resources of calcium hydrogen phosphate fodder for hydrochloric acid and provide more preferable condition.
Summary of the invention
In order to overcome above-mentioned hydrochloric acid to produce the weak point of calcium hydrogen phosphate fodder, manufacturing requirements by the calcium hydrogen phosphate fodder of sustainable development, take into account the full utilization of resources of phosphorus ore, the purpose of the present invention is that the method that a kind of hydrochloric acid of offer produces the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder, the technical scheme is that
A kind of hydrochloric acid produces the production method of the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder, comprises the following steps successively:
A, phosphorus ore generates phosphoric acid, calcium chloride and the solution of Fluohydric acid. with hydrochloric acid reaction, is then peeled off acid non-soluble substance；
B, the phosphoric acid of the hydrofluoric acid containing after separating acid insoluble matter and calcium chloride solution, it is passed through ammonia and carries out fluorine precipitation, generate calcium fluoride precipitate and the phosphoric acid solution of ammonium chloride, carry out solid-liquid separation；
C, separates phosphoric acid and the calcium chloride solution of calcium fluoride precipitate, continues to be passed through ammonia and carries out the precipitation of phosphorus, generates calcium hydrogen phosphate fodder precipitation and the solution of ammonium chloride, then carry out solid-liquid separation.
This method decomposing phosphate rock by chlorhydric acid, separates the siliceous resource of acid non-soluble substance in phosphorus ore；It is not added with any defluorinating agent, with the calcium in phosphorus ore with the form precise precipitation defluorinate of calcium fluoride precipitate, and is enriched with fluorine resource；Supplementary phosphoric acid by wet process makes the calcium chloride in phosphorite stope liquid all as the calcium in calcium hydrogen phosphate fodder product；The calcium carbonate side-product that the carbonate deposition adding ammonia separates is needed specially not for removing calcium chloride.
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, react generation phosphoric acid, calcium chloride and the solution of Fluohydric acid. with hydrochloric acid by above-mentioned reaction equation (1) with the phosphorus ore of fluor-apatite form；The acid non-soluble substance (A.I) of the most most of silicon oxide-containings stays in the solution as solid, and minimal amount of active silica is pressed reaction equation (2) and generated hexafluosilicic acid, and acid non-soluble substance therein can utilize directly as construction material；
In step B, the phosphoric acid of separating acid insoluble matter hydrofluoric acid containing and calcium chloride solution, it is passed through ammonia and carries out the precipitation of fluorine by reaction equation (3) and (4), generate calcium fluoride precipitate and the phosphoric acid solution of ammonium chloride, calcium fluoride is as the fluorine utilization of resources；
In step C, separate phosphoric acid and the calcium chloride solution of calcium fluoride precipitate, continue to be passed through ammonia and carry out the precipitation of phosphorus by reaction equation (5), generate calcium hydrogen phosphate fodder precipitation and the solution of ammonium chloride；The mother solution of described separation calcium hydrogen phosphate fodder, after concentrating, is directly sent to production compound fertilizer, need not be cooled down and Crystallization Separation again.
Wherein, the acid non-soluble substance in step A i.e. silicon compound can utilize directly as construction material；Calcium fluoride in step B is as the fluorine utilization of resources；Calcium hydrogen phosphate in step C can utilize as fertilizer product as feed product, ammonium chloride；So that silicon, fluorine, phosphorus and calcium all obtain Appropriate application.
As preferred technical scheme: in step B, before being passed through ammonia, add the phosphoric acid by wet process produced by sulphuric acid, carry out the calcium in solution/phosphorus mol ratio and calcium/fluorine mol ratio adjusts.Described phosphoric acid by wet process is the phosphoric acid by wet process that sulfuric acid decomposition phosphorus ore produces, and other not calcic phosphoric acid.
Technical scheme as further preferred: in step B, before being passed through ammonia, be additionally added in a part of step C separate calcium hydrogen phosphate fodder precipitation after ammonium chloride solution or washing calcium hydrogen phosphate fodder precipitation washing liquid, the amount of the ammonium chloride solution of return be control add after solution in total phosphorus concentration with P2O5Meter is at 4%-7%P2O5, more preferably 5%-6%P2O5。
As further preferably technical scheme: described calcium/phosphorus mol ratio is 1, and calcium/fluorine mol ratio is 0.5.
As preferred technical scheme: phosphorus ore fineness described in step A is 10-100 mesh, preferably 20-40 mesh；Described hydrochloric acid mass percentage concentration 5%-35%, preferably 15%-30%, hydrochloric acid consumption is the 103%-110% of theoretical decomposition amount.
As preferred technical scheme: in step B, the pH value after ammonification is 0.8-1.6, preferably 1.0-1.4.
As preferred technical scheme: in step C, the pH value after ammonification is 4.0-6.0, preferably 4.5-5.5.
As preferred technical scheme: in step A, B, C, before carrying out solid-liquid separation, carry out in advance settling stiff, and wash with water.
As one preferably technical scheme:
(1) with decomposing phosphate rock by chlorhydric acid, obtain the phosphoric acid of hydrofluoric acid containing and calcium chloride and the mixed liquor of acid non-soluble substance, separate the insoluble solid formation of acid wherein based on silicon oxide, and solid formation filter cake is washed；
(2) mixed liquor after the insoluble solid formation of separating acid, adds the Cake Wash liquid in phosphoric acid by wet process and the ammonium chloride mother liquor of return and technique production, and in adjustment solution, phosphorus content is at 45-60g/LP2O5Between, calcium phosphorus mol ratio Ca/P is 1, and calcium fluorine mol ratio Ca/F is 0.5；Direct ammonia is neutralized precipitation, and making solution pH value is≤1.6, precipitates fluorine with the form of calcium fluoride, reach the fluorine index request of best product quality, its defluorinate liquid phosphorus fluorine ratio >=300, the solid fluorinated calcium of precipitation separation enrichment, and solid fluorinated calcium filter cake is washed；
(3) filtrate separating calcium fluoride directly neutralizes solution pH value >=5.0 again with ammonia, is settled out calcium hydrogen phosphate fodder, carries out solid-liquid separation, and filtration cakes torrefaction obtains product calcium hydrogen phosphate fodder, and washs filter cake；
(4) filtrate isolating calcium hydrogen phosphate is ammonium chloride solution, and part returns precipitation calcium fluoride operation and adjusts control phosphoric acid concentration, and major part, through concentrating, crystallizes as product sale or for production of compound fertilizer.
Compared with prior art, the principle of the present invention and beneficial effect:
Due to the fact that Main Resources element phosphor contained in phosphorus ore, calcium, fluorine, silicon, in the production with hydrochloric acid Fodder making calcium monophosphate product, concentration and separation utilizes with classification respectively, accomplish the atom economy benefit of phosphorus ore, not only reduce the consumption of raw materials during calcium hydrogen phosphate fodder produces, and expand the full resource utilization of phosphorus ore；Shorten again technological process, simplify production equipment, reduce plant investment；Reach to have saved the energy, reduced cost of material, added the economic benefit of Producer and the production purpose of the full utilization of resources of recycling economy without useless pair discharge.The technology of the present invention, shortens technological process, simplifies production equipment, reduces plant investment；Reach to have saved the energy, reduced raw materials for production cost, improved production capacity, reduce investment, increase the economic benefit of Producer, do not had the cleaning of refuse to produce purpose.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that hydrochloric acid of the present invention produces the full utilization of resources of phosphorus ore of calcium hydrogen phosphate fodder.
Detailed description of the invention
Below in conjunction with accompanying drawing, the invention will be further described.
Percentage concentration described in example below, unless stated otherwise, each means mass percentage concentration.
Embodiment 1
As shown in Figure 1: the ground phosphate rock 7000kg/h (composition is shown in Table 1) being milled down to 20-40 mesh through pulverizing is joined acidolysis groove with the hydrochloric acid 15000kg/h that concentration is 25%HCl, carry out the acidolysis reaction of phosphorus ore, after 40 minutes response time, acidolysis slip feeding subsider is settled, bottom underflow material after sedimentation enters pressure filter and separates, filter cake 800kg/h fresh water (FW) washs, obtain the silicon compound product of 2200kg/h aqueous 40%, mix earth as sand for construction material and replace sand material to use.
The filtrate separated from silicon compound pressure filter and cleaning mixture are sent into fluorine stillpot after merging with the top supernatant liquid of subsider, mixed liquor total amount 20600kg/h, the phosphoric acid by wet process (composition is shown in Table 2) adding 6080kg/h gas washing in SA production separates the filtrate 27400kg/h of calcium hydrogen phosphate fodder, washing liquid 4600kg/h and calcium hydrogen phosphate fodder subsider upper clear supernate 10940kg/h with the centrifuge returned, and solution is configured to phosphorus content 5.0%P2O5Concentration, calcium phosphorus molecular proportion Ca/P is 1, and calcium fluorine molecule is 0.5 than Ca/F；It is passed through ammonia and is neutralized reaction precipitation calcium fluoride, when solution pH value reaches 0.8, stop being passed through ammonia, after continuing stirring 15 minutes, the slip of precipitation calcium fluoride is sent into subsider and settles, be simultaneously introduced a small amount of flocculant；Bottom underflow material after sedimentation enters pressure filter and separates, and filter cake 600kg/h fresh water (FW) washs, and obtains the fluorine compounds product of 1020kg/h aqueous 52%, with butt calculating Oil repellent as 37.6%F, is used for replacing fluorite (CaF2) as Fluorine contained chemicals raw materials for production.
The filtrate separated from fluoride pressure filter and washing liquid send into calcium hydrogen phosphate fodder precipitation operation with subsider upper clear supernate after merging, merging mixed liquor total amount is 69200kg/h (mainly comprise and be shown in Table 3), it is passed through ammonia and is neutralized reaction precipitation calcium hydrogen phosphate fodder, when solution pH value reaches 5.0, stop being passed through ammonia, after continuing stirring 20 minutes, the slip of precipitation calcium hydrogen phosphate fodder is sent into subsider and settles；Bottom underflow material after sedimentation enters centrifuge and separates, and filter cake 6300kg/h fresh water (FW) washs, and obtains the calcium hydrogen phosphate fodder product of 8000kg/h aqueous 21%, and with butt calculating phosphorus content as 18.06%P, Oil repellent is 0.11%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 95.8%.
The filtrate 27400kg/h, washing liquid 4600kg/h and the calcium hydrogen phosphate fodder subsider upper clear supernate 10940kg/h return fluorine stillpot that separate from centrifuge are used for diluting after divided silicon compound phosphoric acid solution, add up to；Upper clear supernate 24960kg/h (containing ammonium chloride 22.04%NH from calcium hydrogen phosphate fodder subsider4Cl) send into evaporation concentrator to be evaporated concentrating production ammonium chloride product or being used as production of compound fertilizer raw material, ammonium chloride product 5500kg/h in terms of butt.
Table 2 phosphoric acid by wet process composition 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 |
Table 3 phosphoric acid defluorination mainly comprises
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 4.98 | 0.013 | 7.82 | 14.50 | 167 |
Embodiment 2
As shown in Figure 1: the ground phosphate rock 7000kg/h (composition is shown in Table 4) being milled down to 20-40 mesh through pulverizing is joined acidolysis groove with the hydrochloric acid 22750kg/h that concentration is 21%HCl, carry out the acidolysis reaction of phosphorus ore, after 40 minutes response time, acidolysis slip feeding subsider is settled, bottom underflow after sedimentation enters pressure filter and separates, filter cake 400kg/h fresh water (FW) washs, obtain the silicon compound product of 750kg/h aqueous 60%, mix earth as sand for construction material and replace mortar to use.
The filtrate separated from silicon compound pressure filter and cleaning mixture send into fluorine stillpot after merging with the top supernatant liquid of subsider, merge mixed liquor total amount 29400kg/h, the phosphoric acid by wet process (composition is shown in Table 5) adding 11366kg/h gas washing in SA production separates the filtrate 26833kg/h of calcium hydrogen phosphate fodder, washing liquid 7365kg/h and calcium hydrogen phosphate fodder subsider upper clear supernate 4072kg/h with the centrifuge returned, and solution is configured to phosphorus content 5.50%P2O5Concentration, calcium phosphorus molecular proportion Ca/P is 1, and calcium fluorine molecule is 0.5 than Ca/F；It is passed through ammonia and is neutralized reaction precipitation calcium fluoride, when solution pH value reaches 1.0, stop being passed through ammonia, after continuing stirring 15 minutes, the slip of precipitation calcium fluoride is sent into subsider and settles, be simultaneously introduced a small amount of flocculant；Bottom underflow after sedimentation enters pressure filter and separates, and filter cake 900kg/h fresh water (FW) washs, and obtains the fluorine compounds product of 2284kg/h aqueous 60%, with butt calculating Oil repellent as 40.2%F, is used for replacing fluorite (CaF2) as Fluorine contained chemicals raw materials for production.
After the filtrate separated from fluoride pressure filter and washing liquid merge with subsider upper clear supernate, total amount 77646kg/h (mainly comprise and be shown in Table 6) sends into calcium hydrogen phosphate fodder precipitation operation, it is passed through ammonia and is neutralized reaction precipitation calcium hydrogen phosphate fodder, when solution pH value reaches 5.0, stop being passed through ammonia, after continuing stirring 20 minutes, the slip of precipitation calcium hydrogen phosphate fodder is sent into subsider and settles；Bottom underflow after sedimentation enters centrifuge and separates, and filter cake 11000kg/h fresh water (FW) washs, and obtains the calcium hydrogen phosphate fodder product of 12774kg/h aqueous 18%, and with butt calculating phosphorus content as 17.06%P, Oil repellent is 0.11%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 94.1%.
Return fluorine stillpot be used for diluting after divided silicon compound phosphoric acid solution from the filtrate 26770kg/h of centrifuge separation, washing liquid 11500kg/h, add up to 38270kg/h；Upper clear supernate 38102kg/h (the containing ammonium chloride 24.49%NH of calcium hydrogen phosphate fodder subsider4Cl) send into evaporation concentrator to be evaporated concentrating production ammonium chloride product or being used as production of compound fertilizer raw material, ammonium chloride product 9329kg/h in terms of butt.
Table 4 phosphorus ore composition and content
Table 5 phosphoric acid by wet process composition 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 |
Table 6 phosphoric acid defluorination mainly comprises
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 5.35 | 0.016 | 8.77 | 12.01 | 145 |
Embodiment 3
As shown in Figure 1: the ground phosphate rock 7000kg/h (composition is shown in Table 7) being milled down to 20-40 mesh through pulverizing is joined acidolysis groove with the hydrochloric acid 17257kg/h that concentration is 27%HCl, carry out the acidolysis reaction of phosphorus ore, after 30 minutes response time, acidolysis slip feeding subsider is settled, bottom underflow after sedimentation enters pressure filter and separates, filter cake 500kg/h fresh water (FW) washs, obtain the silicon compound product of 1125kg/h aqueous 60%, mix earth as sand for construction material and replace mortar to use.
The filtrate separated from silicon compound pressure filter and cleaning mixture send into fluorine stillpot after merging with the top supernatant liquid of subsider, merging mixed liquor total amount 23625kg/h, the desulfurization phosphoric acid by wet process (composition is shown in Table 8) that addition 15762kg/h is produced by patent No. ZL94111776.6 technique separates the filtrate 20743kg/h of calcium hydrogen phosphate fodder, washing liquid 11990kg/h with the centrifuge returned and solution is configured to phosphorus content 6.00%P2O5Concentration, calcium phosphorus molecular proportion Ca/P is 1, and calcium fluorine molecule is 0.5 than Ca/F；It is passed through ammonia and is neutralized reaction precipitation calcium fluoride, when solution pH value reaches 1.4, stop being passed through ammonia, after continuing stirring 15 minutes, the slip of precipitation calcium fluoride is sent into subsider and settles, be simultaneously introduced a small amount of flocculant；Bottom underflow after sedimentation enters pressure filter and separates, and filter cake 1200kg/h fresh water (FW) washs, and obtains the fluorine compounds product of 3143kg/h aqueous 65%, with butt calculating Oil repellent as 31.82%F, is used for replacing fluorite (CaF2) as Fluorine contained chemicals raw materials for production.
After the filtrate separated from fluoride pressure filter and washing liquid merge with subsider upper clear supernate, total amount 70180kg/h (mainly comprise and be shown in Table 9) sends into calcium hydrogen phosphate fodder precipitation operation, it is passed through ammonia and is neutralized reaction precipitation calcium hydrogen phosphate fodder, when solution pH value reaches 5.0, stop being passed through ammonia, after continuing stirring 20 minutes, the slip of precipitation calcium hydrogen phosphate fodder is sent into subsider and settles；Bottom underflow after sedimentation enters centrifuge and separates, and filter cake 11000kg/h fresh water (FW) washs, and obtains the calcium hydrogen phosphate fodder product of 11974kg/h aqueous 18%, and with butt calculating phosphorus content as 17.90%P, Oil repellent is 0.14%F.Phosphorous recovery in calcium hydrogen phosphate fodder is 93.2%.
Return fluorine stillpot be used for diluting after divided silicon compound phosphoric acid solution from the filtrate 20743kg/h of centrifuge separation, washing liquid 11990kg/h, add up to 38270kg/h；Upper clear supernate 30936kg/h (the containing ammonium chloride 22.08%NH of calcium hydrogen phosphate fodder subsider4Cl) send into evaporation concentrator to be evaporated concentrating production ammonium chloride product or being used as production of compound fertilizer raw material, ammonium chloride product 6830kg/h in terms of butt.
Table 7 phosphorus ore composition 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 |
Table 8 phosphoric acid by wet process composition 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 |
Table 9 phosphoric acid defluorination mainly comprises
| Composition | P2O5 | F | CaCl2 | NH4Cl | P/F |
| Content (%) | 5.73 | 0.019 | 9.62 | 7.78 | 130 |
Claims (10)
1. the production method of the full utilization of resources of phosphorus ore that a hydrochloric acid produces calcium hydrogen phosphate fodder, it is characterised in that comprise the following steps successively:
A, phosphorus ore generates phosphoric acid, calcium chloride and the solution of Fluohydric acid. with hydrochloric acid reaction, is then peeled off acid non-soluble substance；
B, the phosphoric acid of the hydrofluoric acid containing after separating acid insoluble matter and calcium chloride solution, it is passed through ammonia and carries out fluorine precipitation, generate calcium fluoride precipitate and the phosphoric acid solution of ammonium chloride, carry out solid-liquid separation；
C, separates phosphoric acid and the calcium chloride solution of calcium fluoride precipitate, continues to be passed through ammonia and carries out the precipitation of phosphorus, generates calcium hydrogen phosphate fodder precipitation and the solution of ammonium chloride, then carry out solid-liquid separation.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 1 produces calcium hydrogen phosphate fodder, it is characterized in that: in step B, before being passed through ammonia, add the phosphoric acid by wet process produced by sulphuric acid, carry out the calcium in solution/phosphorus mol ratio and calcium/fluorine mol ratio adjusts.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 2 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 the ammonium chloride solution after separating calcium hydrogen phosphate fodder precipitation or the washing liquid of washing calcium hydrogen phosphate fodder precipitation.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 3 produces calcium hydrogen phosphate fodder, it is characterised in that: described calcium/phosphorus mol ratio is 1, and calcium/fluorine mol ratio is 0.5.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 1 produces calcium hydrogen phosphate fodder, it is characterised in that: phosphorus ore fineness described in step A is 10-100 mesh；Described hydrochloric acid mass percentage concentration 5%-35%, hydrochloric acid consumption is the 103%-110% of theoretical decomposition amount.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 1 produces calcium hydrogen phosphate fodder, it is characterised in that: in step B, the pH value after ammonification is 0.8-1.6.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 1 produces calcium hydrogen phosphate fodder, it is characterised in that: in step C, the pH value after ammonification is 4.0-6.0.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 1 produces calcium hydrogen phosphate fodder, it is characterised in that: in step A, B, C, before carrying out solid-liquid separation, carry out in advance settling stiff, and wash with water.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 5 produces calcium hydrogen phosphate fodder, it is characterised in that: phosphorus ore fineness described in step A is 20-40 mesh；Described hydrochloric acid mass percentage concentration 15%-30%.
The production method of the full utilization of resources of phosphorus ore that a kind of hydrochloric acid the most according to claim 6 produces calcium hydrogen phosphate fodder, it is characterised in that: in step B, the pH value after ammonification is 1.0-1.4.
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| CN114057170A (en) * | 2021-12-20 | 2022-02-18 | 瓮福（集团）有限责任公司 | Method for synthesizing phosphorus pentafluoride and preparing lithium hexafluorophosphate by solid phase method |
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