CN107089648A - The method of hydrochloric acid decomposing medium and low grade process industry phosphoric acid and high-grade calcium chloride - Google Patents
The method of hydrochloric acid decomposing medium and low grade process industry phosphoric acid and high-grade calcium chloride Download PDFInfo
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- CN107089648A CN107089648A CN201610100860.1A CN201610100860A CN107089648A CN 107089648 A CN107089648 A CN 107089648A CN 201610100860 A CN201610100860 A CN 201610100860A CN 107089648 A CN107089648 A CN 107089648A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2208—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid
- C01B25/2212—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with an acid or a mixture of acids other than sulfuric acid with hydrochloric acid or hydrogen chloride in aqueous medium
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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
- C01B25/46—Preparation involving solvent-solvent extraction
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Abstract
A kind of method that the present invention introduces process industry phosphoric acid and high-grade calcium chloride, is to decompose any mid low grade phosphate rock using hydrochloric acid, with milk of lime and decomposed solution, then is extracted with TBP, and industrial phosphoric acid is made in pure water back extraction, concentration.HF is driven in the white fertilizer mashing that raffinate aqueous phase is produced with neutralizing plus hydrochloric acid back dissolving, heating out of, and absorbing reprocessing with water utilizes.Solution cooling salts out metal chloride, and diafiltration, salting-out mother liquor and wash water return to decomposing phosphate rock.Chloride is dissolved with water, plus milk of lime is neutralized, diafiltration, filtrate wash water condensing crystallizing generation anhydrous calcium chloride.The wet solid phase of filtering adds dissolving with hydrochloric acid, with N235Extract iron, absorbing ammonia generates ferric ammonium, iron oxide red is made in blowing air heating in ferric ammonium.Raffinate aqueous phase leads to ammonia and produces magnesium hydroxide, and no boron magnesia is made through diafiltration roasting.Filtrate thermal decomposition after filtering produces alumdum, gas phase cooling generation ammonium chloride.Calcium chloride and white residue are generated into high activity siliceous fertilizer and hydrogen chloride in medium temperature roast, the latter returns to decompose white fertilizer.
Description
Technical field：
It is the phosphoric acid by wet process obtained with decomposing phosphate rock by chlorhydric acid the invention belongs to wet phosphoric acid purifying technology
With the technology category of organic solvent extracting and purifying.
Background technology：
With energy-saving requirement more and more higher, it has been instead of thermal phosphoric acid with Wet Phosphoric Acid Market
The trend of phosphorous chemical industry field development, is mostly purification sulfuric acid wet process phosphoric acid at present, can approach or reach
To the requirement of industrial phosphoric acid, but by industrial phosphoric acid product P2O5Yield only has 80%, and other are low
The fertilizer phosphate of class, can also reach the matter of industrial phosphoric acid from hydrochloric acid wet phosphoric acid purifying in fact
Amount standard, the relatively early and maximum of this respect work is I.M.I mining companies of Israel, only because
Purification sulfuric acid wet process phosphoric acid is turned to a large amount of waste solution of calcium chloride of ocean disposal, domestic East China science and engineering
University, Central China Normal University and Hubei chemical research institute have all made a large amount of R＆D works, but just apply
For patent notes, hydrochloric acid wet phosphoric acid purifying technology category is 200510019049.2 special earliest
Profit, is that industrial phosphoric acid is obtained by extraction with TBP and diisopropyl ether, carried out pilot scale but did not industrialized,
201110006702.7 patent has reached food grade phosphoric acid with a kind of TBP extractions,
201110436529.4 patent uses N235Except iron and TBP extractions have reached food grade phosphoric acid requirement,
Also Chengdu company is asked to be improved due to second-rate.This technique is removed by the step neutralisation of hydrochloric acid two
It is miscellaneous system raise calcium technology enlightenment, using part neutralize decomposing phosphate rock by chlorhydric acid decomposed solution except iron, aluminium,
The method of the impurity such as magnesium, fluorine, lead, a neutralizer is extracted with TBP, it is possible to very convenient
Industrial phosphoric acid has been made.The high-grade phosphorus ore that sulfuric acid wet process sulfuric acid purification industrial phosphoric acid is
(P2O5=30%), P2O5Yield also produces low-grade phosphate fertilizer up to 80%, and this technique is low in using
Grade phosphorus mine (P2O5=6%-17%), P2O5Yield is up to more than 93%, and without low-grade phosphate fertilizer.
The content of the invention：
The present invention is to decompose any phosphorus ore using hydrochloric acid, process industry phosphoric acid and high-grade calcium chloride
Method, is concretely comprised the following steps：
0001 decomposes the full mesh phosphorus ore of mistake 40 with hydrochloric acid, and its reaction temperature is 80 degree Celsius or so, salt
Sour consumption is 105% times of the theoretical acid consumption summation of all metal oxides in phosphorus ore, during reaction
Between for plus miberal powder finish and be stirred for 30 minutes.
0002, with industrial filter cloth heat filtering and washing, obtains decomposed solution and white residue.
0003 in milk of lime and decomposed solution is to PH=1-3, to filter to get filtrate and wet solid phase (white fertile).
0004 filtrate is with TBP: boat coal=1: 1 extractant extraction, and oil phase is with aqueous phase volume ratio
3-5: 1 extraction temperature is 10-45 degree Celsius, and extraction time is 4-5 minutes, is extracted using three cross-flows
Take.
The organic phase that 0005 extraction has phosphoric acid is washed with strip liquor, and consumption is the 3-5% of organic phase volume,
Totally three times, material temperature 10-45 degree Celsius, wash time 5 minutes.
0006 is stripped three times with organic phase volume 10-15% pure water, water temperature 10-45 degree Celsius,
Stripping times 5 minutes.
Strip liquor is concentrated under reduced pressure into P by 00072O5>=62% obtains industrial phosphoric acid.
0008 will be beaten in TBP raffinates aqueous phase and decomposed solution with the wet solid phase (white fertilizer) that produces,
Plus dissolving with hydrochloric acid, the absorber absorption for driving HF gases out of into decomposing phosphate rock by chlorhydric acid process is heated,
Go anhydrous HF processed.
The upper solution of 0009 cooling, separates out a large amount of metal chloride crystallizations, separates, elution, crystallization is female
Liquid and wash water return to decomposing phosphate rock.
The metal chloride of 0010 separation is dissolved in water, and is neutralized with milk of lime and arrives PH=6-7, filtering
Washing, filtrate and wash water condensing crystallizing are into high-grade anhydrous calcium chloride (CaCl2=95.8%).
Add dissolving with hydrochloric acid with the metal hydroxides produced in 0011, with N235Extractant extracts iron.
0012 is passed through gas ammonia in extraction iron organic phase, and the ferric ammonium separating, washing blowing air of generation is roasted
Burn and obtain iron oxide red (Fe2O3=98.2%).
0013 is passed through gas ammonia in extraction iron raffinate aqueous phase, produce magnesium hydrate precipitate, diafiltration, roasting and
Obtain without boron activated magnesia (MgO=95.3%).
The filtrate of 0014 filtering magnesium hydroxide and wash water are produced in 150~250 degree of spray pyrolysis Celsius
Alumdum (Al2O3=95.1%).
Pyrolysis gas phase refrigerated separation is obtained ammonium chloride by 0015.
0016 when calcium chloride dull sale, by crystallization calcium chloride and white residue mix, Celsius
810-820 degree is calcined half an hour, obtains siliceous fertilizer and hydrogen chloride, and the latter returns to acidifying and decomposes white fertilizer.
Brief description of the drawings：
Fig. 1 is hydrochloric acid decomposing medium and low grade process industry phosphoric acid and high-grade calcium chloride process flow
Figure.
The full ground phosphate rock for crossing 40 mesh, which is put into, to be heated in 60 degree Celsius of hydrochloric acid, hydrochloric acid dosage
For 105% times of the theoretical acid consumption summation of phosphorus ore metal oxide, it is incubated and stirs again after miberal powder is finished
Mix 30 minutes, the fluoro-gas of generation is absorbed with water goes anhydrous HF processed, filters while hot, white residue is washed
Stacked after washing, can be used as sand and use, decomposed solution adds milk of lime and neutralized to PH=1-3 while hot,
The wet solid phase (white fertilizer) that removal of impurities is produced is pending, and the decomposed solution that part is neutralized is with TBP: boat coal=1: 1
Extractant extraction, material temperature 10-45 degree Celsius, oil phase: aqueous phase=3-5: 1 extraction time 4-5 minutes,
Cross current solvent extraction three times, oil phase is washed three times with strip liquor, and consumption is the 3-5% of oil phase volume, 5 points
Clock, material temperature is 10-45 degree Celsius, and organic phase is stripped with organic phase volume 10%-15% pure water,
Stripping times are 5 minutes, and water temperature is 10-45 degree Celsius, totally three times, strip liquor is concentrated under reduced pressure
To P2O5>=62% obtains industrial phosphoric acid, is produced in TBP raffinate aqueous phases plus before dissolving with hydrochloric acid
White fertilizer, heat the HF that drives out of and go in the absorber of phosphorus ore decomposition process to absorb anhydrous HF processed, it is cold
But solution separates out a large amount of metal chloride crystallizations, and suction filtration elution, crystallization mother liquor and wash water are returned and decomposed
Phosphorus ore, be dissolved in water this metal chloride, plus milk of lime neutralizes and arrives PH=6-7, produces iron magnalium
Hydroxide, diafiltration, filtrate and wash water concentration granulation produce high-grade anhydrous calcium chloride, by iron aluminium
Magnesium hydroxide adds dissolving with hydrochloric acid, with N235Extractant extraction iron 15 minutes, material temperature 10-45 Celsius
Degree, separates extraction iron organic phase, is passed through gas ammonia, produce ferric ammonium, by the logical sky of ferric ammonium separating, washing
Gas roasting produces iron oxide red, and extraction iron extractant returns to extraction iron next time, the extraction iron raffinate aqueous phase of separation
Ventilation ammonia, is settled out magnesium hydroxide, is calcined and is obtained without boron activated magnesia through diafiltration, filtrate is with washing
Water obtain alumdum in 150~250 degree of spray roastings Celsius, and gas phase cools down to obtain ammonium chloride.
When calcium chloride dull sale, by crystallization calcium chloride and white residue mix, in 810-820 Celsius
Degree roasting half an hour, siliceous fertilizer and hydrogen chloride are obtained, the latter returns to acidifying and decomposes white fertilizer.
Embodiment：
Table 1, raw ore composition
| Title | P2O5 | CaO | MgO | Fe2O3 | Al2O3 | F | Al |
| Weight % | 12.3 | 30.75 | 10.05 | 1.22 | 0.58 | 1.9 | 24.9 |
Claim 1000 grams of full mesh ground phosphate rock of mistake 40, pour into slowly and heated 60 degree 1881 milliliters Celsius
Reacted in 30% technical hydrochloric acid, finish again insulated and stirred 30 minutes, fluoro-gas water, which absorbs, to be gone
Anhydrous HF processed, heat filtering washs to obtain 2490 grams of wet 361 grams of white residue, filtrate and wash water, with lime
Breast neutralize decomposed solution arrive PH=2, suction filtration, 2100 grams of filtrate is with tributyl phosphate: navigate coal=1: 1
6300 milliliters of extractant extractions of volume, 28 degree Celsius of material temperature, extraction time 5 minutes is carried out altogether
Three cross current solvent extractions, load organic phases are with water: 85% phosphoric acid=4: the washing lotion that 1 (volume) is prepared is washed
Wash three times, each consumption is 315 milliliters, when circulate operation is set up, is washed with strip liquor,
26 degree Celsius of water temperature, the organic phase purified with water temperature 26 degree of 630 milliliters of pure water back extraction Celsius,
Totally three times, strip liquor is concentrated under reduced pressure to obtain 178 grams of P2O5=62.3% industrial phosphoric acid.Raffinate aqueous phase
With it is white fertilizer mashing dissolving with hydrochloric acid, heating drive HF out of, into the absorber of decomposing phosphate rock process in inhale
Receive, go anhydrous HF processed, solution cooling separates out a large amount of metal chloride crystallizations, and magma filters elution,
Crystallization mother liquor returns to decomposing phosphate rock with wash water, and metal chloride is dissolved in water, and is neutralized and arrived with milk of lime
PH=6-7, diafiltration, filtrate wash water concentration granulates to obtain 1021 grams of (purity 95.8 of anhydrous calcium chloride
%), metal hydroxides adds dissolving with hydrochloric acid, with N235Extractant extracts iron, and separation extracts iron organic phase,
With ammoniacal liquor back extraction generation ferric ammonium, be isolated washing blowing air be calcined 11.2 grams of purity are
98.2% iron oxide red.It is next that the extractant that ammoniacal liquor back extraction generation ferric ammonium is isolated returns to extraction
The acidifying solution of the metal hydroxides of circulation, raffinate aqueous phase ventilation ammonia during extraction iron, produces hydroxide
Magnesium and aluminate, magnesium hydroxide is filtered, and washing is calcined without 95.2 grams of boron active oxidation magnesium powder
(MgO=95.3%), the solution of filtration washing obtains alumina in 240~250 degree of spray roastings Celsius
Powder (Al2O3=95.1%) 5.5 grams, the NH of gas phase distillation will be calcined4Solid chlorine is collected to obtain in Cl coolings
Change ammonium.By 1021g anhydrous calcium chlorides and the dry white residue mixs of 611g, in 810-820 degree Celsius roasting
Half an hour, high activity siliceous fertilizer 1023g and hydrogen chloride 643g are obtained, by hydrogen chloride negative pressure absorbing in vain
In fertilizer mashing retort, white fertilizer is decomposed.
Table 2, industrial phosphoric acid analysis
Table 3, industrial anhydrous calcium chloride analysis (weight %)
Claims (17)
1. a kind of side with hydrochloric acid decomposing medium and low grade process industry phosphoric acid and high-grade calcium chloride
Method, its feature, method, step are：
Any phosphorus ore is decomposed with technical hydrochloric acid or hydrogen chloride.
2. in milk of lime and decomposed solution is to PH=1-3, to filter to obtain decomposed solution and wet solid phase (white fertile).
3. the method described according to claim 2, with tributyl phosphate: boat coal=1: 1 extraction
Agent is 10-45 degree Celsius, oil phase: aqueous phase=3-4: 1 extracting and purifying decomposed solution 5 minutes in material temperature.
4. method is described according to claim 3, using water: 85% phosphoric acid volume ratio is prepared as 4: 1
Phosphoric acid,diluted, washed during circulate operation with strip liquor by the 3-5% material temperatures 10-45 degree Celsius of oil phase volume
Wash organic phase, 5 minutes.
5. the method described according to claim 4, using 10-45 degree water Celsius as organic phase body
Long-pending 10-15% pure water back extraction organic phase 5 minutes.
6. the method described according to claim 5, P is concentrated under reduced pressure into by strip liquor2O5>=62%
And obtain industrial phosphoric acid.
7. the method described according to claim 2, the raffinate aqueous phase that TBP is extracted and white fertilizer
Hydrochloric acid back dissolving is added in mashing, and heating drives HF out of and removes phosphorus ore decomposition gas absorption plant, together absorbs
Go anhydrous HF processed.
8. the method described according to claim 7, the solution for driving HF out of is cooled to Celsius
20 degree or so, separate out a large amount of metal chloride crystalline solid.
9. the method described according to claim 8, magma is filtered and eluted, filtrate and wash water
Decomposing phosphate rock is returned to, metal chloride reacts with milk of lime, generation iron aluminum-magnesium hydroxide and chlorination
High-grade anhydrous calcium chloride is made with wash water concentration in calcium, suction filtration, washing, filtrate.
10. the method described according to claim 9, by metal hydroxides plus dissolving with hydrochloric acid,
With N235Extractant extracts iron, and material temperature 10-30 degree Celsius extracts 15 minutes, oil phase: aqueous phase=1: 1.
11. the method described according to claim 10, will extract the organic phase separation of iron, lead to ammonia
Generate ferric ammonium, the extractant of separation return iron in the iron magnalium chloride of extraction subsequent cycle from
Son.
12. the method described according to claim 11, ferric ammonium washing blowing air roasting is given birth to
Into iron oxide red and ammonia, ammonia returns to front suction ammonia.
13. the method described according to claim 12, leads to ammonia by extraction iron raffinate aqueous phase, separates out
Magnesium hydrate precipitate and aluminate.
14. the method described according to claim 13, magnesium hydroxide is filtered, wash, roasting
Burn and obtain no boron active oxidation magnesium powder.
15. the method described according to claim 14, by aluminate solution Celsius 150~250
Degree thermally decomposes to generate Al2O3, it is separated into alumdum.
16. the method described according to claim 15, chlorination is collected to obtain by roasting gas phase cooling
Ammonium.
17. the method described according to claim 9, the calcium chloride of separation can with white residue mix,
Half an hour is calcined in 800-1000 degree Celsius, siliceous fertilizer and hydrogen chloride gas is obtained, the latter returns to acidifying
Decompose white fertilizer.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910930A (en) * | 2018-07-04 | 2018-11-30 | 衢州市远方化工厂（普通合伙） | In a kind of energy-efficient calcium hydroxide slurry and the circulation utilization method of mother liquor |
| CN109574048A (en) * | 2019-01-30 | 2019-04-05 | 鲍君杰 | A kind of processing method of discarded lithium iron phosphate positive material |
| CN113387390A (en) * | 2021-08-17 | 2021-09-14 | 赛恩斯环保股份有限公司 | Manganese slag and calcium chloride waste slag recycling method |
-
2016
- 2016-02-18 CN CN201610100860.1A patent/CN107089648A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910930A (en) * | 2018-07-04 | 2018-11-30 | 衢州市远方化工厂（普通合伙） | In a kind of energy-efficient calcium hydroxide slurry and the circulation utilization method of mother liquor |
| CN109574048A (en) * | 2019-01-30 | 2019-04-05 | 鲍君杰 | A kind of processing method of discarded lithium iron phosphate positive material |
| CN109574048B (en) * | 2019-01-30 | 2021-12-10 | 鲍君杰 | Treatment method of waste lithium iron phosphate cathode material |
| CN113387390A (en) * | 2021-08-17 | 2021-09-14 | 赛恩斯环保股份有限公司 | Manganese slag and calcium chloride waste slag recycling method |
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Application publication date: 20170825 |