CN109835935A - Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster - Google Patents
Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster Download PDFInfo
- Publication number
- CN109835935A CN109835935A CN201711207715.4A CN201711207715A CN109835935A CN 109835935 A CN109835935 A CN 109835935A CN 201711207715 A CN201711207715 A CN 201711207715A CN 109835935 A CN109835935 A CN 109835935A
- Authority
- CN
- China
- Prior art keywords
- calcium
- hydrochloric acid
- acid
- filtrate
- calcium salt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to field of feed, and in particular to a method of utilize hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster.Technical problem to be solved by the invention is to provide a kind of methods using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, comprising the following steps: uses hydrochloric acid incomplete decomposing phosphorus ore, the solid was filtered 1 and liquid 1；A, handle solid 1: solid 1 is reacted with hydrochloric acid, is separated by filtration to obtain filter residue and filtrate 2；Sulfuric acid is added in filtrate 2, the heated dechlorination of filtered filtrate 3, defluorinate, dehydration are to get calcium dihydrogen phosphate；B, treatment liquid 1: the fluorine in liquid 1 is 1. removed；2. plus calcium monohydrogen phosphate is made in calcium；3. demagging；4. plus high purity plaster is made in sulfuric acid.The method of the present invention step is easy, and low in cost, the synthos being prepared fully meet national standard, and gained gypsum quality is excellent.
Description
Technical field
The invention belongs to feed and technical field of fertilizers, and in particular to it is a kind of using hydrochloric acid and Phosphate Rock acid calcium salt and
The method of high purity plaster.
Background technique
Synthos can be used as fertilizer grade synthos, be widely used in agricultural production, be mainly used as configuration compound fertilizer
Raw material, farmland can also be directly applied to；Synthos can be used as feed-grade calcium phosphate salt, be suitable for the animals such as livestock and poultry, aquatic products,
It is a kind of for supplementing the feed addictive of livestock and poultry, aquatic livestock calcium phosphorus nutrition.
P is generally believed in industry2O5It is middle-low grade phosphate in 24%-28%, 18%-24% is low-grade phosphate ore.Chinese phosphorus
Ore resources are relatively abundanter, have verified total resources and have been only second to Morocco, have occupied second place of the world.Phosphorite Resources in China generally has
Have following main feature: reserves are larger, and distribution is concentrated；Middle and low grade bauxite is more, and rich ore is few, and Chinese phosphorus ore grade is poor, P2O5
Average content is 17% or so, and rich ore only accounts for about the 85% of rock phosphate in powder total amount, therefore the phosphorus ore of most of China has to pass through choosing
The demand of phosphoric acid and high concentration phosphorus composite heat transfer is just able to satisfy after mine rich ore；Difficult ore dressing is more, and easy ore dressing is few, stores up in Chinese phosphorus ore
In amount, appositional pattern phosphorus block salt (collophane) is more, and the 85% of Zhan Quanguo gross reserves, wherein most is middle-low grade ore, simultaneously
Chinese phosphorus ore 90% is high-magnesium-phosphorus ore, and the fine size of valuable mineral and gangue are tightly combined in ore, is not readily separated, China
Rock phosphate in powder one of the rock phosphate in powder that hardly possible is selected in the world.
Production feed grade or the method for fertilizer synthos, which are mostly first reacted using sulfuric acid with phosphorus concentrate, at present generates wet process
Phosphoric acid, phosphoric acid by wet process is by pretreatment, defluorinate purification, then reacts with calcium sources such as calcium carbonate and generate synthos slurry, through high temperature
Atomization drying obtains qualified products.The process flow is complicated, at high cost, to the bad adaptability of phosphorus ore raw material.Patent
CN105921259A discloses a kind of method for generating feed-level calcium biphosphate using middle-low grade mixing rock phosphate in powder, seems and adopts
It uses mid low grade phosphate rock as raw material, however actually still will sequentially add suppression in the middle-low grade calcium and magnesium matter rock phosphate in powder ore pulp
Preparation and collecting agent, reverse flotation, be made phosphorus concentrate further with sulfuric acid reaction.The technique of existing production synthos is big simultaneously
The calcium in phosphorus ore is first mostly converted to ardealite (the very high calcium sulfate of impurity) as trade waste to exclude, ardealite
Stockpiling and digestion are the difficult points of the industry, have influenced the sustainable development of the industry, and in subsequent production synthos
Need to be added a large amount of calcium carbonate etc. again in the process as calcium source, to cause the significant wastage of resource.
Summary of the invention
Hydrochloric acid and Phosphate Rock acid calcium salt and high-purity stone are utilized technical problem to be solved by the invention is to provide a kind of
The method of cream.Method includes the following steps:
With the hydrochloric acid incomplete decomposing phosphorus ore below of mass concentration 15%, it is separated by filtration to obtain solid 1 and liquid 1；Wherein,
Mass ratio P in solid 12O5/ MgO > 6；
A, handle solid 1: solid 1 is reacted with hydrochloric acid, is separated by filtration to obtain filter residue and filtrate 2；In filtrate 2 be added sulfuric acid into
Row reaction, is obtained by filtration filter cake 3 and filtrate 3；It is gypsum after filter cake 3 is dry；Filtrate 3 heat dechlorination, defluorinate, dehydration to get
Calcium dihydrogen phosphate；
B, treatment liquid 1:
1. alkaline calcium salt is added in liquid 1 adjusts pH to 1.2~2.2, it is separated by filtration to obtain filter cake 4 and filtrate 4；
2. alkaline calcium salt is added in filtrate 4 adjusts pH to 4.8~6.2, it is separated by filtration to obtain filter cake 5 and filtrate 5, filter cake 5
As calcium monohydrogen phosphate；
3. alkaline calcium salt is added in filtrate 5 adjusts pH to 9~11, it is separated by filtration to obtain filter cake 6 and filtrate 6；
4. filtrate 6 and sulfuric acid reaction obtain high purity plaster and hydrogen chloride or hydrochloric acid.
Specifically, it is above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, control sulfuric acid
Additional amount be so that excessive calcium is fully converted to calcium sulfate；The excessive calcium refers to that phosphoric acid and calcium are converted into phosphorus in filtrate 2
Remaining calcium after acid dihydride calcium.
Preferably, above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, sulfuric acid is added
React while keeping the temperature, holding temperature is 60~100 DEG C.
Preferably, above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, the solid
1 with hydrochloric acid CaO ︰ HCl=1 ︰ 0.8~3 according to the molar ratio.Further, the solid 1 and hydrochloric acid CaO ︰ HCl according to the molar ratio
=1 ︰ 1.6~2.4.
Preferably, above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, the hydrochloric acid
Mass concentration 5% or more.Further, the mass concentration of the hydrochloric acid is 20~30%.
Specifically, above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, the solid
1 with hydrochloric acid reaction temperature be room temperature~80 DEG C.
Preferably, above-mentioned using in the method and step A of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, the heating
Dechlorination, defluorinate, dehydration are using any one realization in negative pressure concentration, oven drying, atomization, disk or cylinder.
Specifically, it is above-mentioned using in the method and step B of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster 1., the alkali
Property calcium salt be at least one of lime or calcium carbonate.
Specifically, it is above-mentioned using in the method and step B of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster 2., the alkali
Property calcium salt be at least one of lime or calcium carbonate.
Specifically, it is above-mentioned using in the method and step B of hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster 3., the alkali
Property calcium salt be at least one of quick lime or white lime.
The method of the present invention has the advantages that
1, since dilute hydrochloric acid incomplete decomposing phosphorus ore has the function of removing magnesium addition, there are also remove in processing step B
The unit of the impurity such as iron, aluminium, magnesium is not only applicable to high-grade phosphorus ore and phosphorus concentrate, especially suitable for height in the process of the present invention
The mid low grade phosphate rock of impurity eliminates the process investment to the selected processing of raw material phosphorus ore；Since mid low grade phosphate rock reserves are big
Price is low, therefore this technique has significant cost advantage.
2, calcium monophosphate product is made in processing step B by calcium dihydrogen phosphate is made in processing step A for the method for the present invention,
Two kinds of product compounding processing can be obtained into di-calcium phosphate product, so, the implementation of this technique can disposably obtain three
Kind synthos product.
3, the calcium of phosphorus ore is completely converted into the calcium of ionic state in the method for the present invention, the calcium of phosphoric acid and ionic state in step A
It can sufficiently react, not generate package, biphosphate calcium product purity is high, free acid content is low, and subsequent product is prevented from caking, quality
It is excellent, meet GBT22548-2008 to feed-level calcium biphosphate requirement.
4, the available two kinds of chemical gypsums of the implementation of the method for the present invention, wherein height phosphorous, that fluorine is especially low is made in step B
Pure gypsum can be further processed into high-intensitive α gypsum or whisker gypsum product, walk gypsum made from poly- A can produce plus
Work β building gypsum, and Tao Mo gypsum can be gone out by two kinds of gypsum mixed preparings of α, β, meet the needs of different clients market.
5, phosphorus of (or whole) phosphorus of the part in the synthos that the method for the present invention is prepared in phosphorus ore, this portion
Divide P2O5It is obtained not over sulfuric acid preparing phosphoric acid, to not generate reluctant ardealite, reduces the row of trade waste
It puts, implements this technique with high Social benefit and economic benefit.
6, the method for the present invention step A completes dechlorination, defluorinate, dehydration and promotion product by heating a process
Four purposes are produced, production efficiency is improved, realize the efficient production of synthos；Step A is not necessarily to additional defluorinating agent simultaneously
Chemical defluorinate is carried out, process is optimized, has saved cost.
7, the method for the present invention generate hydrochloric acid can closed circulation recycle, reduce exhaust emissions, not will cause environment
Pollution, while reducing the consumption to other production factors, there is high economic benefit and environmental benefit.
Detailed description of the invention
The process flow diagram of Fig. 1 the method for the present invention
Specific embodiment
A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, comprising the following steps:
With the hydrochloric acid incomplete decomposing phosphorus ore below of mass concentration 15%, it is separated by filtration to obtain solid 1 and liquid 1；Wherein,
It counts in mass ratio, P in solid 12O5/ MgO > 6；This step purpose is to remove most magnesium, magnesium in phosphorus ore to enter liquid 1, phase
When in further purifying to phosphorus ore, 1 impurities of solid obtained from are less, be conducive to filter cake carry out step A reaction and
Obtain the calcium dihydrogen phosphate of good quality；Contain Ca in liquid 12+、H2PO4 -、Cl-、F-, magnesium-ferrum-aluminum plasma；
A, handle solid 1: solid 1 is reacted with hydrochloric acid, is separated by filtration to obtain filter residue and filtrate 2；In filtrate 2 be added sulfuric acid into
Row reaction, is obtained by filtration filter cake 3 and filtrate 3；It is gypsum after filter cake 3 is dry；Filtrate 3 heat removing system in hydrogen chloride,
Hydrogen fluoride and water, and calcium dihydrogen phosphate is produced simultaneously, so that qualified calcium dihydrogen phosphate is made in a step；
B, treatment liquid 1:
1. alkaline calcium salt is added in liquid 1 provides calcium source, regulation system pH to 1.2~2.2 keeps fluorine in system and calcium anti-
CaF should be generated2, to achieve the purpose that defluorinate, it is separated by filtration to obtain 4 defluorination residues of filter cake and filtrate 4；
2. alkaline calcium salt is added in filtrate 4 provides calcium source, regulation system pH to 4.8~6.2 make phosphate radical in system with
Calcium reacts to obtain calcium monohydrogen phosphate precipitating, is separated by filtration to obtain filter cake 5 and filtrate 5, and filter cake 5 is calcium monohydrogen phosphate, dry, collection filter
Cake 5；
3. alkaline calcium salt is added in filtrate 5 adjusts pH to 9~11, the impurity magnesium ion in system is made to be precipitated as hydroxide
Magnesium, while also reaching a small amount of iron in removing system, aluminum ions purpose, it is separated by filtration to obtain 6 de-magging slag of filter cake and 6 chlorination of filtrate
Calcium solution；
4. the concentration of 6 calcium chloride solution of filtrate obtains high purity plaster and hydrogen chloride then with sulfuric acid reaction for calcium chloride slurry
Or hydrochloric acid.
In the method for the present invention, used raw material phosphorus ore be high impurity phosphorus ore, phosphorus concentrate, senior middle school's low-grade phosphate ore,
Effective component is Ca5F(PO4)3.P is generally believed in industry2O5It is middle-low grade phosphate 24~28%, 18~24% be low product
Position phosphorus ore, being higher than 28% is high-grade phosphorus ore.
In the method for the present invention, incomplete decomposing described in hydrochloric acid incomplete decomposing phosphorus ore refers to: when decomposing phosphate rock by chlorhydric acid,
Phosphorus in phosphorus ore is not fully converted to acid soluble phosphorus.Influence decomposing phosphate rock by chlorhydric acid degree factor include phosphorus ore activity,
Granularity, reaction temperature, reaction time, hydrochloric acid and proportion of phosphorus ore of phosphorus ore etc., control incomplete decomposing can from it is above-mentioned it is several because
Element is adjusted, and those skilled in the art can be according to condition possessed by phosphorus ore type, production actual demand and production etc., flexibly
Ground adjusts from any of the above or several factors, selects, controls phosphorite stope raw material granularity, reaction temperature time, raw material
The parameters such as proportion, to control phosphorus ore incomplete decomposing, and also need to meet P in solid 1 simultaneously2O5/ MgO mass ratio > 6.If
The meaning for counting this step is to remove the magnesium in phosphorus ore, improves phosphorus ore purity, be conducive to improve final product quality.Control salt
It is allocation proportion in order to control phosphorus in solid phase and liquid phase in incomplete acidolysis reaction that the mass concentration of acid, which is 15% or less,；Control
P2O5/ MgO mass ratio > 6 is to guarantee that the resulting biphosphate calcium product of step A is up-to-standard.
In the method for the present invention, the separation of solid and liquid is are as follows: the system after hydrochloric acid incomplete decomposing phosphorus ore is separated,
Solid and liquid are separated, the separate mode of this field routine, such as filtering, stiff, standing, centrifugation mode can be used.When adopting
When with the mode of filtering, filter cake is solid 1 of the invention, and filtrate is liquid 1 of the invention；When by the way of stiff
When, thickener can be used and carry out stiff, through the isolated thick slurry of thickener and clear liquid, thick slurry is solid 1 of the invention, clear liquid
Liquid 1 as of the invention；When by the way of standing, the slurry of lower layer is solid 1 of the invention, the supernatant on upper layer
Liquid 1 as of the invention.The present invention is separated by solid-liquid separation the mode that the combinations such as filtering, stiff, standing, centrifugation can also be used, such as quiet
The mode that filters after filtering, stiff etc. is postponed, as long as separation liquid and solid or slurry can be reached.
In the method for the present invention step A, hydrochloric acid dosage is not particularly limited, but such as hydrochloric acid dosage is excessively high, will increase equipment
Load is also unfavorable for later period HCl recovery, wastes raw material simultaneously；If hydrochloric acid dosage is too low, it is incomplete to will cause decomposing phosphate rock, point
Solution rate is low, and phosphorus ore is caused to waste.It is preferred, therefore, that, according to the molar ratio, the calcium in solid 1 controls solid 1 and hydrochloric acid based on CaO
CaO ︰ HCl=1 ︰ 0.8~3.It is further preferred that CaO ︰ HCl=1 ︰ 1.6~2.4.
In the method for the present invention step A, the phosphorus ore that hydrochloric acid decomposes in solid 1 is easy to carry out, and at normal temperature, hydrochloric acid quality is dense
Degree is 20~30%, and general a few minutes being capable of complete decomposing phosphate rock.So step A decomposing phosphate rock by chlorhydric acid to the concentration of hydrochloric acid,
Reaction temperature, reaction time are all not particularly limited.Less salt acid concentration also can decomposing phosphate rock, but need to extend the reaction time and/or
Reaction temperature is increased, and hydrochloric acid dosage increases, is unfavorable for later period heating dechlorination, defluorinate, dehydration, increases machine utilization, increase energy
Consumption；Equally, reaction temperature is lower, then needs using concentrated hydrochloric acid and/or extend the reaction time；But concentration of hydrochloric acid, reaction temperature,
Reaction time only influences reaction efficiency, does not influence on the quality of products obtained therefrom itself.Consider from efficiency, economy etc., it is excellent
Select the mass concentration of hydrochloric acid 5% or more.Further, the mass concentration of hydrochloric acid is 20~30%.Preferable reaction temperature room temperature
, reaction temperature can also centainly be adjusted according to needs of production, such as controlling reaction temperature is room temperature~80 DEG C.
In the method for the present invention step A, the purpose that sulfuric acid is added is excessive calcium in precipitation filtrates 2, and the excessive calcium is
Refer to that phosphoric acid and calcium are converted into remaining calcium after calcium dihydrogen phosphate in filtrate 2.In fact, when sulfuric acid being additionally added in step A, itself
There are the phosphoric acid in filtrate 2 not to generate calcium dihydrogen phosphate with calcium, herein excludes the part calcium simply by theoretical calculation, remains
Remaining calcium is that additional sulfuric acid is needed to react generation calcium sulfate.
For example, from the point of view of theoretical amount, it is assumed that after measured, 3mol phosphoric acid and 5mol chlorine are contained in filtrate 2 obtained by step A
Change calcium, heating defluorinate, dechlorination, dehydration products obtained therefrom are calcium dihydrogen phosphate, and 3mol phosphoric acid needs to consume 1.5mol calcium, then there remains
3.5mol calcium, 3.5mol calcium herein are then excessive calcium, then need to be added 3.5mol sulfuric acid and react with excessive 3.5mol calcium,
To which products therefrom is calcium dihydrogen phosphate.It should be understood that above-mentioned data are theoretical amounts, in actual operation and instead
During answering, there may be certain deviation, as long as actually guaranteeing that the product synthos being prepared are up-to-standard.
In addition, according to practical factory the needs of calcium sulfate can be controlled with the amount of the calcium sulfate of production, that is, control sulfuric acid
Additional amount.When needing lower to calcium sulfate, the sulfuric acid amount of addition can also not exclusively make excessive calcium be converted into calcium sulfate, then
Phosphoric acid is added and reacts generation calcium dihydrogen phosphate with remaining excessive calcium, avoids calcium in product excessively high, to be made up-to-standard
Biphosphate calcium product.
It further, is middle strong acid strong acid since calcium chloride generates calcium dihydrogen phosphate and reacting for hydrochloric acid with phosphatase reaction
Reaction, if phosphoric acid and calcium ion ratio are just reacted completely only according to theoretical calculation may cause reaction for reversible reaction
It is not thorough, causes biphosphate calcium product unqualified.So in step A, such as adding in order to guarantee that product is qualified in actual production
Enter phosphoric acid, then needing to be added excessive phosphoric acid makes remaining excessive calcium be fully converted to calcium dihydrogen phosphate, heated dechlorination, de-
After fluorine, dehydration, phosphoric acid neutralizer, which is added, makes remaining phposphate calcium dihydrogen phosphate.Or the amount of sulfuric acid is added than theoretical meter
Calculation amount is higher, then makes in filtrate that remaining calcium is relatively smaller, phosphoric acid is relatively more.The phosphoric acid neutralizer be lime,
At least one of calcium carbonate, calcium phosphate.
In above method step A, heat preservation separation can prevent product to be precipitated, and improve the yield and calcium sulfate of calcium dihydrogen phosphate
Purity, while reducing subsequent step energy consumption.
In above method step A, when addition sulfuric acid reacts generation calcium sulfate with calcium ion, a small amount of intermediate might have
It generates, if temperature is slightly lower, intermediate can be parsed, so that the yield that will lead to calcium dihydrogen phosphate decreases.So the step
It can also be kept the temperature, temperature is 60~100 DEG C.Such as the step is not kept the temperature, and is only reduction of the yield of calcium dihydrogen phosphate, and right
The quality of calcium dihydrogen phosphate does not influence.
In above method step A, the heating dechlorination, defluorinate, dewatering type are not particularly limited, as long as can make system
In water, hydrogen chloride, hydrogen fluoride remove, thus make reaction to the right carry out, using negative pressure concentration, atomization, disk, cylinder etc.
Usual manner, as acid extraction according to different heating methods and depending on decomposing synthos.This hair
Bright method and step A, due to the reduction of hydrogen chloride, promotes above-mentioned reaction and carries out to the right, be equivalent in dechlorination, defluorinate, dehydration
One one step of heating stepses has reached dechlorination, defluorinate, dehydration simultaneously and product is promoted to generate four purposes, is different from conventional add
Enter the chemical mode that defluorinating agent removes fluorine, not only easy to operate, saving step, but also eliminate the use of a large amount of defluorinating agent, saves
About raw material, and obtain the biphosphate calcium product haveing excellent performance.
In the liquid 1 of the method for the present invention step B, contain Ca2+、H2PO4 -、Cl-、F-, magnesium-ferrum-aluminum plasma, in order to
To the calcium monophosphate product of good quality, need to remove the foreign ion such as F in filtrate-, magnesium-ferrum-aluminum plasma, first exogenously added alkali
Property calcium salt control pH to 1.2~2.2 obtain the composite precipitation of calcirm-fluoride and iron aluminium, so that filtering and removing fluorine and part iron aluminium are miscellaneous
Matter；Then phosphate radical is precipitated out by additional alkaline calcium salt control pH again for 4.8~6.2, obtains product calcium monohydrogen phosphate；Then again
Additional alkaline calcium salt control pH is the magnesium in 9~11 precipitation systems；Finally for the calcium chloride in recovery system, it is added after concentration
Sulfuric acid reaction is up to the higher gypsum of purity, so that this step has reached removing impurity, recycles the mesh of useful ionized calcium, phosphate radical
, and products obtained therefrom calcium monohydrogen phosphate and gypsum purity are high, excellent quality.
The hydrogen chloride that the method for the present invention step A, B generates can be recycled for decomposing phosphate rock, to realize hydrogen chloride
It is recycled, has saved cost.
Main reaction equation involved in the method for the present invention step A is as follows:
Phosphorite stope: Ca5F(PO4)3+10HCl→3H3PO4(acidolysis)+5CaCl2+HF↑
Chemical equation when heating dechlorination, defluorinate, dehydrating prods are calcium dihydrogen phosphate:
5CaCl2+3H3PO4(acidolysis)+3.5H2SO4(additional) → 1.5Ca (H2PO4)2+3.5CaSO4(filtering) ↓+10HCl
Main reaction equation involved in the method for the present invention step B is as follows:
Defluorinate: Ca2++F-→CaF2↓
DCP is generated: Ca2++PO4 3-→CaHPO4
Demagging: Mg2++OH-→Mg(OH)2↓
Embodiment 1-4
According to the form below 1 selects phosphorus ore, and the following table 2 controls each step material rate relationship.With decomposing phosphate rock by chlorhydric acid 30min, filtering
Separate to obtain filter cake 1 and filtrate 1；
Step A: hydrochloric acid is added and decomposes filter cake 1, the amount that hydrochloric acid is added is calculated according to the CaO in filter cake 1, after reacting 30min
Stiff separation, slurry return to acidleach part and react again together with thick slurry, calcium ion, phosphate anion are contained in filtrate 2, according to life
At the P of calcium dihydrogen phosphate2O5/ CaO is additionally added sulfuric acid precipitation and obtains calcium sulfate, and washing obtains high-quality gypsum, and remaining liq is through mist
Change defluorinate, dechlorination, dehydration, obtains qualified biphosphate calcium product.
Step B, it is 1.2~2.2 progress defluorinate removal of impurities that alkaline calcium salt control pH, which is added, in filtrate 1, then adds alkaline calcium
Salt adjust pH value be 4.8~6.2 in and obtained synthos product, however through alkaline calcium salt adjust pH to 9~11 remove MgO,
98% sulfuric acid is added after concentrated and generates crystal of calcium sulfate, filtration washing obtains high purity plaster, the synchronous dilute hydrochloric acid reuse generated
To diluted acid acidolysis process decomposition phosphorus ore.Acquired results see the table below 2-7.
1 phosphorus ore index of table
| P2O5% | CaO% | MgO% | Fe2O3% | Al2O3% | SiO2% | F% | SO4 2-% | H2O% |
| 28.32 | 40.98 | 1.58 | 1.63 | 1.43 | 13.84 | 2.66 | 0.54 | 1.00 |
Table 2
Table 3
Table 4
Table 5
Table 6
Table 7
It in summary it can be seen, the method for the present invention calcium monohydrogen phosphate produced, calcium dihydrogen phosphate, gypsum are superior to national mark
It is quasi-.
Claims (9)
1. utilizing the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, it is characterised in that: the following steps are included:
With the hydrochloric acid incomplete decomposing phosphorus ore below of mass concentration 15%, it is separated by filtration to obtain solid 1 and liquid 1；Wherein, solid
Mass ratio P in 12O5/ MgO > 6；
A, handle solid 1: solid 1 is reacted with hydrochloric acid, is separated by filtration to obtain filter residue and filtrate 2；Sulfuric acid is added in filtrate 2 to carry out instead
It answers, filter cake 3 and filtrate 3 is obtained by filtration；It is gypsum after filter cake 3 is dry；Filtrate 3 heats dechlorination, defluorinate, dehydration to get phosphoric acid
Calcium dihydrogen；
B, treatment liquid 1:
1. alkaline calcium salt is added in liquid 1 adjusts pH to 1.2~2.2, it is separated by filtration to obtain filter cake 4 and filtrate 4；
2. alkaline calcium salt is added in filtrate 4 adjusts pH to 4.8~6.2, it is separated by filtration to obtain filter cake 5 and filtrate 5, filter cake 5 is
Calcium monohydrogen phosphate；
3. alkaline calcium salt is added in filtrate 5 adjusts pH to 9~11, it is separated by filtration to obtain filter cake 6 and filtrate 6；
4. filtrate 6 and sulfuric acid reaction obtain high purity plaster and hydrogen chloride or hydrochloric acid.
2. the method according to claim 1 using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, feature exist
In: in step A, the additional amount for controlling sulfuric acid is that excessive calcium is made to be fully converted to calcium sulfate；The excessive calcium refers to filtrate 2
Middle phosphoric acid and calcium are converted into remaining calcium after calcium dihydrogen phosphate.
3. the method according to claim 1 using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, feature exist
In: in step A, sulfuric acid is added and react while keeping the temperature, holding temperature is 60~100 DEG C.
4. the method according to claim 1 using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, feature exist
In: in step A, the solid 1 and hydrochloric acid CaO ︰ HCl=1 ︰ 0.8~3 according to the molar ratio；Further, the solid 1 and salt
Sour CaO ︰ HCl=1 ︰ 1.6~2.4 according to the molar ratio.
5. the method according to claim 1 or 4 using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster, feature
Be: in step A, the mass concentration of the hydrochloric acid is 5% or more；Further, the mass concentration of the hydrochloric acid be 20~
30%.
6. described in any item methods using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster according to claim 1~5,
It is characterized by: the heating dechlorination, defluorinate, dehydration use negative pressure concentration, oven drying, atomization, disk or circle in step A
Any one realization in cylinder.
7. described in any item methods using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster according to claim 1~6,
It is characterized by: in step B 1., the alkaline calcium salt is at least one of lime or calcium carbonate.
8. described in any item methods using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster according to claim 1~6,
It is characterized by: in step B 2., the alkaline calcium salt is at least one of lime or calcium carbonate.
9. described in any item methods using hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster according to claim 1~6,
It is characterized by: in step B 3., the alkaline calcium salt is at least one of quick lime or white lime.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711207715.4A CN109835935A (en) | 2017-11-27 | 2017-11-27 | Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster |
| PCT/CN2017/117517 WO2019100499A1 (en) | 2017-11-27 | 2017-12-20 | Method for producing calcium phosphate salt and high-purity gypsum by using hydrochloric acid and phosphate rock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711207715.4A CN109835935A (en) | 2017-11-27 | 2017-11-27 | Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109835935A true CN109835935A (en) | 2019-06-04 |
Family
ID=66631795
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711207715.4A Pending CN109835935A (en) | 2017-11-27 | 2017-11-27 | Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN109835935A (en) |
| WO (1) | WO2019100499A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467213A (en) * | 2019-09-11 | 2019-11-19 | 武汉工程大学 | A method of calcium sulfate crystal whiskers are prepared using High-Mg phosphate tailings |
| CN111017894A (en) * | 2019-12-31 | 2020-04-17 | 云南力达一矿物技术有限公司 | Method for preparing clean phosphoric acid and high-purity gypsum by decomposing ground phosphate rock with hydrochloric acid |
| CN113845137A (en) * | 2020-06-28 | 2021-12-28 | 湖北省绿盛坤环保科技有限公司 | Method for producing high-purity white phosphogypsum from high-impurity-content phosphorite |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527877A (en) * | 1978-08-22 | 1980-02-28 | Chisso Corp | Production of high purity calcium secondary phosphate and ammonium chloride |
| CN1789116A (en) * | 2004-12-14 | 2006-06-21 | 自贡鸿鹤化工股份有限公司 | Method for producing phosphorous acid and gypsum using hydrochloric acid method |
| CN1803589A (en) * | 2006-01-25 | 2006-07-19 | 四川省犍为明丰化工有限公司 | Method for producing feed grade dicalcium phosphate and industrial grade phosphoric acid by phosphate ore hydrochloric acid reclamation process |
| CN101434386A (en) * | 2007-11-12 | 2009-05-20 | 黄明科 | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using |
| CN103496685A (en) * | 2013-10-14 | 2014-01-08 | 四川省化工设计院 | Method for continuously producing feed-grade dibasic calcium phosphate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3652206A (en) * | 1969-01-17 | 1972-03-28 | American Cyanamid Co | Defluorinated calcium phosphate compositions, and method of preparing and using same |
| US7687046B2 (en) * | 2002-06-28 | 2010-03-30 | Ecophos | Method of producing phosphoric acid salt |
| CN102583290A (en) * | 2012-02-18 | 2012-07-18 | 张黔生 | Low-grade phosphorite mineral dressing technology and method for producing by-product high-purity gypsum powder |
| CN106044732B (en) * | 2016-06-05 | 2018-06-08 | 禄丰天宝磷化工有限公司 | A kind of method that double phosphate rock-sulfuric acids make calcium monohydrogen phosphate |
| CN107043956A (en) * | 2017-04-19 | 2017-08-15 | 湖北三宁化工股份有限公司 | A kind of method of hydrochloric acid and phosphorus mine tailing extracting sulfuric acid calcium pyroborate and magnesium hydroxide |
-
2017
- 2017-11-27 CN CN201711207715.4A patent/CN109835935A/en active Pending
- 2017-12-20 WO PCT/CN2017/117517 patent/WO2019100499A1/en active Application Filing
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5527877A (en) * | 1978-08-22 | 1980-02-28 | Chisso Corp | Production of high purity calcium secondary phosphate and ammonium chloride |
| CN1789116A (en) * | 2004-12-14 | 2006-06-21 | 自贡鸿鹤化工股份有限公司 | Method for producing phosphorous acid and gypsum using hydrochloric acid method |
| CN1803589A (en) * | 2006-01-25 | 2006-07-19 | 四川省犍为明丰化工有限公司 | Method for producing feed grade dicalcium phosphate and industrial grade phosphoric acid by phosphate ore hydrochloric acid reclamation process |
| CN101434386A (en) * | 2007-11-12 | 2009-05-20 | 黄明科 | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using |
| CN103496685A (en) * | 2013-10-14 | 2014-01-08 | 四川省化工设计院 | Method for continuously producing feed-grade dibasic calcium phosphate |
Non-Patent Citations (1)
| Title |
|---|
| 雷兴家: ""盐酸-硫酸分步分解磷矿石的初步研究"", 《湖北化工》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110467213A (en) * | 2019-09-11 | 2019-11-19 | 武汉工程大学 | A method of calcium sulfate crystal whiskers are prepared using High-Mg phosphate tailings |
| CN111017894A (en) * | 2019-12-31 | 2020-04-17 | 云南力达一矿物技术有限公司 | Method for preparing clean phosphoric acid and high-purity gypsum by decomposing ground phosphate rock with hydrochloric acid |
| CN111017894B (en) * | 2019-12-31 | 2022-05-10 | 云南力达一矿物技术有限公司 | Method for preparing clean phosphoric acid and high-purity gypsum by decomposing ground phosphate rock with hydrochloric acid |
| CN113845137A (en) * | 2020-06-28 | 2021-12-28 | 湖北省绿盛坤环保科技有限公司 | Method for producing high-purity white phosphogypsum from high-impurity-content phosphorite |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019100499A1 (en) | 2019-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109836177A (en) | A method of utilizing hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster | |
| CN101337657A (en) | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer | |
| CN105367176A (en) | Multi-element comprehensive utilization process for phosphorus-potassium associated ore | |
| CN107814370B (en) | Circulating environment-friendly process method for preparing phosphate concentrate, product and application thereof | |
| CN109835935A (en) | Utilize the method for hydrochloric acid and Phosphate Rock acid calcium salt and high purity plaster | |
| CN103496685A (en) | Method for continuously producing feed-grade dibasic calcium phosphate | |
| CN103539165B (en) | Method for producing potassium sulfate by utilizing insoluble rocks containing potassium | |
| CN104909841A (en) | Process for preparing calcium magnesium ammonium phosphate and calcium magnesium ammonium nitrate through nitric acid decomposition of low-medium graded phosphate ore | |
| CN105197905A (en) | Production method for extracting phosphorite cogeneration feed grade monocalcium phosphate and industrial grade monoammonium phosphate | |
| CN101318845A (en) | Process for preparing potash magnesium sulphate fertilizer with kalium containing sulfate | |
| WO2013174062A1 (en) | Method for pre-treating phosphorus rock by mixture of titanium dioxide waste acid and fluorine-containing waste water | |
| CN102502553A (en) | Method for preparing feed grade calcium hydrogen phosphate from waste water of phosphate fertilizer plant | |
| CN101434386A (en) | Method for producing fine phosphate by using dilute acid to decompose middle and low grade phosphate ore using | |
| CN100503440C (en) | Process of preparing potassium sulfate with potassium containing bittern of magnesium sulfate subtype | |
| CN105110308A (en) | Phosphorite comprehensive utilization method | |
| CN104744175A (en) | Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore | |
| CN104944561A (en) | Wastewater nitrogen and phosphorus removing method based on magnesite | |
| CN105110352A (en) | Method for producing potassium sulfate from potassium/chlorine-ion-containing solid waste | |
| CN110395702A (en) | The method of phosphoric acid by wet process coproduction ammonium dihydrogen phosphate and calcium hydrophosphate fodder | |
| CN105417515A (en) | Co-production method of feed-grade calcium phosphate dibasic and fertilizer-grade monoammonium phosphate | |
| CN104692436A (en) | Method for preparing cryolite from coal ash | |
| CN107793180A (en) | Improve the method for magnesium leaching efficiency and application in phosphorus ore | |
| CN105293459A (en) | Method for producing fully water-soluble monoammonium phosphate and co-producing ammonium magnesium phosphate by wet process phosphoric acid | |
| CN104828799B (en) | Process of producing feed-grade calcium dihydrogen phosphate through phosphoric acid circulation impurity removal method | |
| CN109399594A (en) | A kind of cleaning method of mid low grade phosphate rock powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190604 |