CN110482507A - A kind of method of metal ion in reduction raffinate - Google Patents
A kind of method of metal ion in reduction raffinate Download PDFInfo
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- CN110482507A CN110482507A CN201910730502.2A CN201910730502A CN110482507A CN 110482507 A CN110482507 A CN 110482507A CN 201910730502 A CN201910730502 A CN 201910730502A CN 110482507 A CN110482507 A CN 110482507A
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- hydrofluoric acid
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- 238000000034 method Methods 0.000 title claims abstract description 50
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 13
- 239000007788 liquid Substances 0.000 claims abstract description 18
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 56
- 239000002253 acid Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 7
- ZWYDDDAMNQQZHD-UHFFFAOYSA-L titanium(ii) chloride Chemical compound [Cl-].[Cl-].[Ti+2] ZWYDDDAMNQQZHD-UHFFFAOYSA-L 0.000 claims description 7
- 239000011737 fluorine Substances 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 229960002050 hydrofluoric acid Drugs 0.000 claims 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 3
- 229910052739 hydrogen Inorganic materials 0.000 claims 2
- 239000001257 hydrogen Substances 0.000 claims 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000002222 fluorine compounds Chemical class 0.000 claims 1
- 125000001153 fluoro group Chemical group F* 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- -1 aluminum ions Chemical class 0.000 abstract description 2
- 239000011777 magnesium Substances 0.000 abstract description 2
- 229910052749 magnesium Inorganic materials 0.000 abstract description 2
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 abstract 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract 1
- 229910001425 magnesium ion Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 24
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 12
- 238000000746 purification Methods 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009388 chemical precipitation Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000003337 fertilizer Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000011928 denatured alcohol Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 1
- 235000019796 monopotassium phosphate Nutrition 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000002686 phosphate fertilizer Substances 0.000 description 1
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/234—Purification; Stabilisation; Concentration
- C01B25/237—Selective elimination of impurities
- C01B25/238—Cationic impurities, e.g. arsenic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a kind of methods of metal ion in reduction raffinate, it is characterized in that, include the following steps: to be put into raffinate in thermostat water bath and is heated to 40~70 DEG C, the mixture of ammonium hydroxide and fluorochemical is added, after being stirred to react 1~4h, 12~36h is stood, it is raffinate that clear liquid, which is obtained by filtration,.This method simple process, it is easy to operate, it is that one is aluminum ions methods in effective and feasible reduction raffinate without being transformed to existing equipment.The raffinate handled through the method for the present invention, magnesium, aluminium ion have obtained preferable removal effect: wherein magnesium ion removal rate is up to 20~49%, and aluminium ion removal rate is up to 30~54%.
Description
Technical field
The present invention relates to a kind of new methods of metal ion in reduction raffinate, belong to wet phosphoric acid purifying field.
Background technique
Phosphoric acid is daily necessity and industrial important industrial chemicals, can be used for producing phosphate fertilizer, feed nutrition agent, food
Additive etc., phosphoric acid play critically important role in mankind's activity.The method of production phosphoric acid mainly has thermal method and wet process work
Skill, but thermal method technique has apparent defect, and energy consumption is high, and environmental pollution is serious, and energy consumption is about 3 times of wet process.As society is fast
Speed development, the wet method phosphoric acid manufacture process advantage of the more aobvious protrusion of energy crisis, low energy consumption gradually shows, and gradually substitutes high energy
Consumption, seriously polluted thermal method technique.
There are many wet phosphoric acid purifying technologies studied both at home and abroad at present, mainly have chemical precipitation method, solvent precipitation,
Ion-exchange, crystallisation, concentration method and solvent extraction etc..Compared with other methods, solvent extraction has many advantages, such as,
Such as good product quality, process are simple, cost is relatively low, the rate of recovery is high, environmental pollution is small, easy realization automates etc., this method
It is external one of the most effectual way for being used to purification of wet process phosphoric acid, and uniquely can be realized heavy industrialization obtains method.
The principle of solvent extraction is that phosphoric acid dissolves in organic solvent, and other impurity do not dissolve in solvent, to make
Phosphoric acid is separated with impurity.The water phase of organic phase and phosphoric acid can be obtained using this method, wherein water phase is known as raffinate, due to it
Complicated component, impurity content are high, and purposes is limited only to fertilizer production.Although raffinate can be used for producing fertilizer, fertilizer production
Device also necessary synchronized construction, constrains the production of purifying phosphoric acid.Therefore purifying and recycle raffinate is that raising purification is wet
The most effective approach of method phosphoric acid plant production capacity.
There is P using the raffinate that solvent extraction obtains2O5Content is high, foreign ion is more and content it is high (metal impurities from
Son is 1.5~2 times of raw material phosphoric acid), the features such as solid content is big, viscosity is big, thus the purification difficulty of raffinate is very big.
The report of the purification in relation to phosphoric acid both at home and abroad is mainly solvent precipitation at present, such as patent GB464370 is proposed
In the presence of a small amount of alkali metal or ammonium compounds, water-miscible solvent is added, into phosphoric acid solution with precipitated impurities.Suitable
Organic solvent is 92% ethyl alcohol, methylated spirit or acetone.
Patent GB1342344 discloses a kind of method for purifying phosphoric acid.Potassium dihydrogen phosphate is first added in concentrated phosphoric acid, then is added
It is a kind of to make contamination precipitation with the organic liquid (such as methanol, isopropanol, methyl ethyl ketone) of water complete miscibility；From containing the organic of phosphoric acid
Phase rectifying Separation of Organic is purified phosphoric acid.
United States Patent (USP) US4152402 discloses a kind of method using acetone purifying phosphoric acid, contains 30%P2O5Phosphoric acid by wet process
It is mixed with acetone and ammonia；Settle and separate；Rectifying upper solution obtains product phosphoric acid, and rectifying lower layer solution obtains impure phosphorus
Acid.
China Patent Publication No. CN1039800C discloses a kind of improved method of solvent sedimentation method for purifying wet method phosphoric acid,
It is characterized in that solvent used is the mixed solvent containing ethyl alcohol, butanol.
China Patent Publication No. CN101708830A discloses a kind of purification method of raffinate, it is added in raffinate
3-5 times of volume of mixed solvent is stood after reaction, is obtained by filtration clear liquid, clear liquid vacuum degree 0.08MPa, temperature 60 C~
It is distilled to recover alcohol at 80 DEG C, is purified raffinate.
Existing solvent precipitation processing phosphoric acid condition is more simple, and impurity content is limited, cleans more single, and process is cumbersome,
Thus it is not applied for the purification of raffinate.
Summary of the invention
It is an object of the invention to overcome disadvantage mentioned above to provide, a kind of removal of impurities range is wide, effect is good, the simple raffinate of process
The purification method of acid.
The technical solution of the present invention is as follows: a kind of method for reducing metal ion in raffinate, which is characterized in that including as follows
Step: raffinate being put into thermostat water bath and is heated to 40~70 DEG C, and the mixture of ammonium hydroxide and fluorochemical is added,
After being stirred to react 1~4h, 12~36h is stood, it is raffinate that clear liquid, which is obtained by filtration,.
In above scheme, the P of the raffinate2O5Content is 43%~48%, content of MgO 3%, Al2O3Content is
3.5%。
In above scheme, the temperature is 40~70 DEG C, preferably 50~65 DEG C.
In above scheme, the mixture additive amount of the ammonium hydroxide and fluorochemical is the 5%~10% of raffinate quality,
The molar ratio of ammonium hydroxide and fluorine in fluorochemical is 4~8 in mixed solution.
The mass concentration of the ammonium hydroxide is 22-32%, and the mass concentration of fluorochemical is 15-20%.
Fluorochemical include fluosilicic acid, hydrofluoric acid, graphene-supported hydrofluoric acid, titanium dichloride load hydrofluoric acid,
The hydrofluoric acid of MOF material load.
In the hydrofluoric acid of graphene-supported hydrofluoric acid, titanium dichloride load, the hydrofluoric acid of MOF material load, hydrofluoric acid
Load capacity be 0.5-1%.
The preparation method of the hydrofluoric acid of graphene-supported hydrofluoric acid, titanium dichloride load, the hydrofluoric acid of MOF material load
It is as follows:
Reaction flask is added in 100ml acetone, graphene (can be replaced titanium dioxide or MOF) 10g and 50 μ g-100 μ g of hydrofluoric acid
In, reaction mixture under an argon, 40-50 DEG C of stirring 12-20h.Product through filtering, water washing, 80 DEG C of vacuum drying 3-4h,
Obtain solid product.As corresponding graphene-supported hydrofluoric acid, the hydrofluoric acid of titanium dichloride load, MOF material load
Hydrofluoric acid.
In above scheme, the reaction time is 1~4h, preferably 2h；The time of repose is 12~36h, excellent
It is selected as 20h.
The method that the present invention uses chemical precipitation, may be containing ingredients such as ammonia, ammonium fluoride, fluosilicic acid in precipitating reagent, can be with
Chemical precipitation reaction, such as magnesium, aluminium, potassium, sodium, iron etc. occur for various metals ion in raffinate, and foreign ion removal rate is 20%
~54%, only separation need to can be realized using simple physical filtering in good purification, the sediment of generation.With solvent precipitation
Compare, the present invention has purification range wide, good purification, the beneficial effects such as process is simple to operation, is a kind of effective and feasible
Raffinate purification method.
Specific embodiment
The present invention is further described combined with specific embodiments below, but is not limited to embodiment.
Embodiment 1: taking 100g raffinate stoste, be placed in 55 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 8g mixed solution is added thereto, ammonium hydroxide and fluosilicic acid molar ratio are 5:1 in mixed solution, sufficiently reaction 2h is stirred, then
It stands for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.70%, Fe2O3Content 0.36%, content of MgO 2.15%, corresponding ion removal efficiency point
It Wei 50%, 20%, 35%.
Embodiment 2: taking 100g raffinate stoste, be placed in 60 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 6g sodium fluoride is added thereto, ammonium hydroxide and fluosilicic acid molar ratio are 6:1 in mixed solution, stir sufficiently reaction 2h, then quiet
It sets for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.93%, Fe2O3Content 0.36%, content of MgO 2.4%, corresponding ion removal efficiency difference
It is 42%, 20%, 28%.
Embodiment 3: taking 100g raffinate stoste, be placed in 50 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 10g hydrogen fluoride is added thereto, ammonium hydroxide and fluosilicic acid molar ratio are 7:1 in mixed solution, sufficiently reaction 2h is stirred, then
It stands for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.90%, Fe2O3Content 0.34%, content of MgO 2.2%, corresponding ion removal efficiency difference
It is 43%, 24%, 34%.
Embodiment 4: taking 100g raffinate stoste, be placed in 55 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 8g mixed solution is added thereto, (load capacity of hydrofluoric acid is for ammonium hydroxide and graphene-supported hydrofluoric acid in mixed solution
0.65%) molar ratio is 5:1, stirs sufficiently reaction 2h, then stand for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.82%, Fe2O3Content 0.32%, content of MgO 2.11%, corresponding ion removal efficiency point
It Wei 45%, 28%, 37%.
Embodiment 5: taking 100g raffinate stoste, be placed in 55 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 8g mixed solution is added thereto, the hydrofluoric acid (load capacity of hydrofluoric acid of ammonium hydroxide and titanium dichloride load in mixed solution
It is 5:1 for 0.4%) molar ratio, stirs sufficiently reaction 2h, then stand for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.72%, Fe2O3Content 0.30%, content of MgO 1.94%, corresponding ion removal efficiency point
It Wei 48%, 33%, 42%.
Embodiment 6: taking 100g raffinate stoste, be placed in 55 DEG C of thermostat water bath and heat, and rises to setting temperature to temperature
After degree, 8g mixed solution is added thereto, the hydrofluoric acid (load capacity of hydrofluoric acid of ammonium hydroxide and MOF material load in mixed solution
It is 5:1 for 0.8%) molar ratio, stirs sufficiently reaction 2h, then stand for 24 hours, upper layer is raffinate clear liquid.
Al in raffinate stoste2O3Content is 3.35%, Fe2O3Content is 0.45%, content of MgO 3.35%.Obtained extraction
It is Al that spent acid clear liquid, which converts index,2O3Content 1.52%, Fe2O3Content 0.28%, content of MgO 1.68%, corresponding ion removal efficiency point
It Wei 54%, 37%, 49%.
Claims (8)
1. a kind of method for reducing metal ion in raffinate, which comprises the steps of: raffinate is put into constant temperature
It is heated to 40~70 DEG C in water-bath, the mixture of ammonium hydroxide and fluorochemical is added, after being stirred to react 1~4h, stands
12~36h, it is raffinate that clear liquid, which is obtained by filtration,.
2. the method according to claim 1 for reducing metal ion in raffinate, it is characterised in that: the raffinate
P2O5Content is 43%~48%, and content of MgO is 3~4.2%, Al2O3Content is 3.3~4.5%.
3. the method according to claim 1 for reducing metal ion in raffinate, it is characterised in that: raffinate is in water-bath
In be heated to temperature be 50~65 DEG C.
4. it is according to claim 1 reduce raffinate in metal ion method, it is characterised in that: the ammonium hydroxide with contain
The mixture additive amount of fluorine compounds is the 5%~10% of raffinate quality, ammonium hydroxide and fluorine in fluorochemical in mixed solution
Molar ratio is 4~8.
5. the method according to claim 1 for reducing metal ion in raffinate, it is characterised in that: the quality of the ammonium hydroxide
Concentration is 22~32%, and the mass concentration of fluorochemical is 15~20%.
6. the method according to claim 1 or 4 or 5 for reducing metal ion in raffinate, it is characterised in that: fluorine-containing chemical combination
Object includes the hydrogen fluorine of fluosilicic acid, hydrofluoric acid, graphene-supported hydrofluoric acid, the hydrofluoric acid of titanium dichloride load, MOF material load
Acid.
7. the method according to claim 6 for reducing metal ion in raffinate, it is characterised in that: graphene-supported hydrogen
Fluoric acid, the hydrofluoric acid of titanium dichloride load, MOF material load hydrofluoric acid in, the load capacity of hydrofluoric acid is 0.5~1%.
8. it is according to claim 1 reduce raffinate in metal ion method, it is characterised in that: be added ammonium hydroxide with it is fluorine-containing
The mixture of compound after being stirred to react 2h, stands 20h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4639359A (en) * | 1985-12-16 | 1987-01-27 | International Minerals & Chemical Corp. | Process of removing cationic impurities from wet process phosphoric acid |
| CN101704518A (en) * | 2009-12-15 | 2010-05-12 | 瓮福（集团）有限责任公司 | Method for purifying raffinate acid |
| CN101708830A (en) * | 2009-12-15 | 2010-05-19 | 瓮福（集团）有限责任公司 | Method for purifying raffinate |
| CN103523764A (en) * | 2013-06-27 | 2014-01-22 | 云南云天化国际化工股份有限公司 | Method for reducing magnesium and aluminum impurities in wet-process phosphoric acid |
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