CN103641093A - Phosphoric acid desulphurization or/and defluorination method for ammonium biphosphate industrial production - Google Patents
Phosphoric acid desulphurization or/and defluorination method for ammonium biphosphate industrial production Download PDFInfo
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Abstract
The invention provides a phosphoric acid desulphurization or/and defluorination method for ammonium biphosphate industrial production. The invention relates to an inorganic chemical technology field. The method comprises: according to an amount of 100-105%, adding calcium oxide or calcium hydrate required by reacting sulfate radical and fluorinion respectively with calcium hydrate, into dilute phosphoric acid obtained in the reaction of sulfuric acid with fluor apatite for the ammonium biphosphate industrial production, stirring at medium and high speed in 800-3000 r/min, filtrating to separate gypsum, calcium fluoride or/and metasilicic acid, magnesium hydroxide, iron hydroxide and aluminium hydroxide, and carrying out desulphurization and/or defluorination. The method is applied in industrial production of an ammonium biphosphate agricultural composite fertilizer.
Description
Affiliated technical field:
The present invention relates to inorganic chemistry industrial technology field, especially in primary ammonium phosphate industrial production phosphoric acid desulfurization or/and the method for defluorinate.
Background technology:
Primary ammonium phosphate agricultural composite fertilizer is large small profits industrial goods, and product major impurity is the water-soluble MgSO being brought by fluoro-containing apatite powder and sulfuric acid reaction
4, Al
2(SO
4)
3, Fe
2(SO
4)
3and hydrogen fluoride; And associated minerals SiO in HF and floats
2be combined into again the SiF of gaseous state
4if HF is excessive, SiF
4further generate again H
2siF
6.SiF
4can be hydrolyzed to again positive silicic acid (H
4siO
4) and HF; Positive silicic acid (H
4siO
4) be water-fast white gelatinous precipitate, be also insoluble to phosphate aqueous solution.In fluoro-containing apatite powder, also contain sulfuric acid insolubles silicon-dioxide and/or limonite.
And prior art does not also have removal H applicable and that produce for primary ammonium phosphate agricultural composite fertilizer
3pO
4middle vitriol and hydrofluoric acid (HF) are or/and SiF
4the method of efficient cheapness.The content of vitriol in primary ammonium phosphate product, up to more than 12%, has significantly reduced primary ammonium phosphate product water-soluble nitrogen and P
2o
5content.HF and silicon tetrafluoride gas pollutant atmosphere; Silicon tetrafluoride hydrolysis simultaneously generates water-soluble silicic acid and enters primary ammonium phosphate product, has reduced primary ammonium phosphate product water-soluble nitrogen and P
2o
5content.That biphosphate ammonium compound fertilizer has significant damage to environment in producing is a large amount of HF and the SiF certainly leading to
4gas.
In primary ammonium phosphate industrial production, F is mainly with SiF
4there is H in phosphoric acid with HF form
2siF
6content seldom, even if there is H
2siF
6generate, because its acidity is also stronger than sulfuric acid, so its many reaction with phosphatic rock generates CaSiF
6and enter phosphogypsum slag.
In actual primary ammonium phosphate is produced for making H
2sO
4fully react with fluoro-containing apatite, temperature of reaction is many more than 80 ℃, and in fluoro-containing apatite, dioxide-containing silica is higher, so H
3pO
4middle fluoride pollution is mainly a large amount of SiF
4and HF, H
2siF
6content seldom.
In existing primary ammonium phosphate industrial production, vitriol and SiF
4, HF, H
2siF
6simultaneous (sulfuric acid reacts at 80 ℃ above with fluoro-containing apatite).
Prior art desulfurization: (one). use CaCO
3/ BaCO
3/ floats are removed H
3pO
4in vitriol, CaCO
3result of use is poor, BaCO
3poisonous and cost is high; Floats not only result of use are poor, also brought new pollution substance into.H
3pO
4sulfuric acid in the aqueous solution is that above-mentioned three kinds of vitriol hydrolysis produces, and concentration is little, is difficult to be eliminated.
(2). Chinese patent, application number 200910061556.0, open (bulletin) day: 2009.09.09, open (bulletin) number: CN101525130.
With adding CaO and ground phosphate rock by the 140-160% of sulfate ion stoichiometric ratio, CaO: ground phosphate rock=4--9:1, turns desulfurization under the condition of-250 revs/min at 40 ℃-50 ℃, stirring velocity 200; From its CaO input amount, analyze, only with the minimum input amount of CaO, calculate, its consumption has surpassed the actual generation of sulfate radical CaSO
4the more than 92% of required CaO consumption, consumption is too large, has run counter to scientific common sense.And it turns under-250 revs/min of conditions at 40 ℃-50 ℃, 200 and stir, because its rotating speed is too slow, CaO is Ca (OH)
2skewness in phosphate aqueous solution, CaO is Ca (OH)
2content is too much again, and this will cause a large amount of H
3pO
4by reaction, generated CaHPO
4or Ca
3(PO
4)
2, cause H
3pO
4waste, and produced unnecessary water-insoluble CaHPO
4or Ca
3(PO
4)
2waste residue will produce a large amount of water-soluble Ca (H in phosphate aqueous solution simultaneously
2pO
4)
2.Reaction times is also oversize, 210-240min; Both reduce the production efficiency of enterprise, also aggravated CaHPO
4or Ca
3(PO
4)
2the generation of water-insoluble waste residue.This patent (application) technology does not solve CaO or Ca (OH)
2at H
3pO
4in the aqueous solution, remove the great side effect difficult problem that vitriol must solve, particularly in primary ammonium phosphate industrial production.The Sodium Silicofluoride precipitation that this patent (application) technology generates for sodium carbonate is reacted with silicofluoric acid, drops to 40 ℃-50 ℃ (with 40 ℃ time sedimentation effect best) by phosphate aqueous solution temperature; And the phosphate aqueous solution temperature after dihydrate gypsum filtration is 65 ℃ of left and right in existing primary ammonium phosphate industrial production, significantly cooling will consume a large amount of energy; In order to realize the ammoniumization reaction of phosphoric acid, again phosphate aqueous solution temperature is risen to 65 ℃ of left and right again, consume again a large amount of energy.The inapplicable primary ammonium phosphate industrial production of this patent (application) technology.
Prior art defluorinate, (one). Chinese patent, application number 200910061556.0, open (bulletin) day: 2009.09.09, open (bulletin) number: CN101525130.
Press the 100-120% of fluorion stoichiometric ratio, add defluorinating agent Na
2cO
3, adding activated silica auxiliary agent simultaneously, this is that HF is changed into H
2siF
6again with Na
2cO
3effect generates Na
2siF
6precipitation (at 40 ℃-50 ℃).Na
2cO
3with activated silica auxiliary agent (diatomite), all can greatly increase the production cost of enterprise, and primary ammonium phosphate agricultural composite fertilizer is small profits or meagre profit, bulk product.Poisonous Na
2siF
6waste residue and H
3pO
4in remaining poisonous water-soluble Na
2siF
6, Ye Gei enterprise has increased insoluble burden, causes again primary ammonium phosphate product to contain poisonous Na
2siF
6composition, and serious threat soil and water surrounding.And in phosphoric acid, also have SiF
4pollute, this method can not be removed SiF
4.
(2) Chinese patent (application), application number 99114891.6, open (bulletin) day: 2000.11.29, open (bulletin) number: CN1274679, unauthorized.
With CaO:CaCO
3=(0.9-1.1): (3.6-4.4) proportioning defluorinate.CaO is at CaO/CaCO
3in defluorinating agent, only account for 20% left and right; CaCO
3can not remove SiF
4, its efficiency and effect that removes HF in industrial production is also poor, can only remove H
2siF
6; CaO proportioning consumption very little, can not better remove HF and SiF
4.It is Ca (OH) that this patent application does not solve CaO equally
2at H
3pO
4in the aqueous solution with H
3pO
4generate water-insoluble CaHPO
4or Ca
3(PO
4)
2great technical barrier, but directly avoided this great technical barrier that must solve; Only symbolically adopted a small amount of CaO, to avoid too much CaHPO
4or Ca
3(PO
4)
2generate, but lack, stop CaHPO
4or Ca
3(PO
4)
2the necessary technique means generating will produce a certain amount of water-soluble Ca (H in phosphate aqueous solution simultaneously
2pO
4)
2.
And it adopts in two sections and defluorinate, secondary supernatant, flash trapping stage, recycle acid molten (HF acid and H
2siF
6) method; Can only be for the defluorinate of industrial phosphoric acid, and can not require high biphosphate ammonium compound fertilizer to produce for large, streamline operration.
The production of industrial phosphoric acid ammonium dihydrogen agricultural composite fertilizer is in the urgent need to efficient cheap, nontoxic, practical disposable defluorinate and the method for desulfurization, and solves CaO or Ca (OH)
2at H
3pO
4desulfurization in the aqueous solution is or/and the water-insoluble CaHPO that defluorinate generates
4/ Ca
3(PO
4)
2h
3pO
4loss technical barrier.
Summary of the invention:
Principle of the present invention:
One, HF in the aqueous solution below 80 ℃ with (HF) of hydrogen bonded
nassociated complex form exists, and can not dissociate H
+and F
-ion, and not with SiO
2reaction generates SiF
4or H
2siF
6.
Two, with SO
4 2-and F
-caO or Ca (OH) that ion or HF calculate
2in middle and high speed stirs, due to H
3pO
4be weak acid, there is hardly oxidisability, and HF/H
2sO
4all than H
3pO
4oxidisability is strong, HF/H
2sO
4with H
3pO
4to with Ca (OH)
2effect forms strong competitive relation; Due to CaO or Ca (OH)
2with SO
4 2-and F
-ion or HF calculate, and overall control, as long as also have H
2sO
4/ SO
4 2-/ HF exists, Ca (OH)
2just can only generate CaSO with vitriol, sulfuric acid (vitriol hydrolysis) and hydrofluoric acid (HF) effect
4and CaF
2.Due to CaO/Ca (OH)
2overall control, under middle and high speed stirs, Ca (OH)
2in phosphate aqueous solution, be evenly distributed, even if there is a small amount of Ca (OH)
2with H
3pO
4effect, HF is or/and H so
2sO
4just seem excessive, and due to H
3pO
4weak acid, its H
+ion divides three step ionization, like this in middle and high speed stirs, due to Ca (OH)
2wretched insufficiency amount, so a small amount of Ca (OH)
2with excessive H
3pO
4can only generate water miscible Ca (H
2pO
4)
2, and Ca (H
2pO
4)
2again with excessive HF (hydrofluoric acid) or H
2sO
4reaction generates CaF
2or CaSO
4, and restore H
3pO
4(weak acid), so just can not cause H
3pO
4generate CaHPO
4/ Ca
3(PO
4)
2phosphorus loss.Silicofluoric acid H
2siF
6acid stronger than sulfuric acid, more easily by calcium hydroxide reaction, generated calcium silicofluoride, and be eliminated; Competing reaction principle is identical.
Three, under middle and high speed stirs, mechanical energy can be converted into chemical energy, and the oxidisability of hydrofluoric acid (HF) strengthens greatly; Simultaneously under high-speed stirring, the intermolecular hydrogen bond of HF is destroyed, and exists with the HF molecular form dissociating; Ca (OH)
2be again highly basic, acid-base neutralisation strong reaction, is conducive to remove HF.
Four, vitriol Mg SO
4, Fe
2(SO
4)
3and Al
2(SO
4)
3, in hot water, hydrolysis generates H
2sO
4, Mg (OH)
2, Fe (OH)
3and Al (OH)
3; Phosphoric acid is weak acid, Mg (OH)
2, Fe (OH)
3and Al (OH)
3be insoluble to the dilute phosphoric acid aqueous solution, as long as H
2sO
4by Ca (OH)
2be reacted into CaSO
4or gypsum, so above-mentioned three kinds of vitriol will be generated water-insoluble CaSO by complete hydrolysis
4/ gypsum, Mg (OH)
2, Fe (OH)
3and Al (OH)
3, and be eliminated.MgSO
4, Fe
2(SO
4)
3and Al
2(SO
4)
3also can be respectively and Ca (OH)
2reaction generates CaSO
4or gypsum, Mg (OH)
2, Fe (OH)
3and Al (OH)
3, and be eliminated.Sulfate radical SO
4 2-with phosphoric acid H
3pO
4also be competitive relation.
Five, chemical reaction the principles of science and industrial machinery the principles of science are combined closely, to reach the effect of getting twice the result with half the effort.CaO or Ca (OH) limit the quantity of
2stir and depend on each other for existence with middle and high speed, a complicated difficult problem is simplified, thoroughly solve H
3pO
4a salt precipitation technology difficult problem and the technical barrier of desulfurization, the disposable processing of defluorinate.
Sulfate radical can detect according to prior art, also can to the detection data of magnesium oxide, ferric oxide and alumina content in fluoro-containing apatite, be converted into respectively Mg SO according to prior art
4, Fe
2(SO
4)
3and Al
2(SO
4)
3and obtain the total mass number of sulfate radical.
Hydrogen fluoride and silicon tetrafluoride can detect according to prior art, also can to the detection data reduction of fluorine content in fluoro-containing apatite, become HF according to prior art.
The present invention is equally applicable to the production of Secondary ammonium phosphate agricultural fertilizer.
" inverse ratio " of the present invention refers to that one of them amount increases, and another amount just can reduce; Otherwise one of them measures minimizing, another amount just can increase; Rather than strict mathematical meaning.
For overcoming the defect of prior art, the invention provides a kind of for phosphoric acid desulfurization in the industrial production of primary ammonium phosphate agricultural composite fertilizer or/and the method for defluorinate.
The technical solution adopted for the present invention to solve the technical problems is:
(1). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 65 ℃--and 79 ℃, hydrogen fluoride is existed in associated complex (HF) the n form with hydrogen bonded below 80 ℃, reduce the water solubility of silicon-dioxide simultaneously, do not generate silicon tetrafluoride or silicofluoric acid with silicon dioxde reaction, stop the generation of the positive silicic acid of silicon tetrafluoride hydrolysis yet; Sulfuric acid reacts in employing with fluoro-containing apatite, low double speed mix and blend, makes sulfuric acid fully contact with phosphatic rock, fully react fast; Stirring at low speed 300 turns-400 revs/min; Middling speed stirs 600 and turns-800 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and hydrogen fluoride content in the phosphoric acid material pulp aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--102% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In phosphate aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(2). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃--and 100 ℃, rotating speed 300 turns-400 revs/min, reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and fluorine content in the dilute phosphoric acid slip aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter; Comprise HF and SiF
4in fluorine; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and HF comparison, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide, aluminium hydroxide and positive silicic acid in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the phosphate aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(3). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃--and 100 ℃, during sulfuric acid and fluoro-containing apatite reactor adopt or high and low double speed mix and blend; Stirring at low speed 300 turns-400 revs/min; Middle and high speed stirs 800 revs/min-1500 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. detect sulfate radical anion concentration and hydrogen fluoride in the dilute phosphoric acid slip aqueous solution in above-mentioned (one), silicon tetrafluoride content; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the sulfuric acid and fluoro-containing apatite reactor of above-mentioned (one), and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; With middle and high speed, stir, 800 revs/min-1500 revs/min of stirring velocitys, and turn-400 revs/min with stirring at low speed 300 and carry out simultaneously, churning time 120 minutes-180 minutes, stirring velocity and time are inversely proportional to; Stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and the comparison of HF content, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), positive silicic acid, calcium silicofluoride, magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer; Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
Beneficial effect:
1. the present invention has greatly improved the total content of the water-soluble available nitrogen of primary ammonium phosphate agricultural composite fertilizer, Vanadium Pentoxide in FLAKES, can reach more than 63%, surpasses the high-content standard of 60% country; And the total content of nitrogen, Vanadium Pentoxide in FLAKES is 55% in the primary ammonium phosphate of existing containing sulfate and silicic acid agricultural composite fertilizer, this is national minimum standard.
2. the present invention has effectively protected atmospheric environment, greatly reduce or stopped primary ammonium phosphate produce in the discharge of hydrogen fluoride or silicon tetrafluoride toxic gas.
3.. the present invention has significantly improved the economic benefit of enterprise.
4. chemical raw material of the present invention is easy to get, and production cost is low, and save energy is produced and processed simply; Processing waste residue is nontoxic, and waste and the environmental pollution of natural fluorine, magnesium, iron and bauxite resource have been avoided in easily separated recovery; Be applicable to the production of large-scale industry primary ammonium phosphate agricultural composite fertilizer.
5. the middle and high fast stirring reaction step of sulfuric acid of the present invention and fluoro-containing apatite reactions steps, calcium hydroxide or calcium oxide and combination thereof are that core technology of the present invention innovates essential features.
Preferred version of the present invention:
(1). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 75 ℃, hydrogen fluoride is existed in associated complex (HF) the n form with hydrogen bonded below 80 ℃, reduce the water solubility of silicon-dioxide simultaneously, do not generate silicon tetrafluoride or silicofluoric acid with silicon dioxde reaction, stop the generation of the positive silicic acid of silicon tetrafluoride hydrolysis yet; Sulfuric acid reacts in employing with fluoro-containing apatite, low double speed mix and blend, makes sulfuric acid fully contact with phosphatic rock, fully react fast; 400 revs/min of stirring at low speed; Middling speed stirs 800 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and hydrogen fluoride content in the phosphoric acid material pulp aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 102% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In phosphate aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(2). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 85 ℃, 400 revs/min of rotating speeds, reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and fluorine content in the dilute phosphoric acid slip aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter; Comprise HF and SiF
4in fluorine; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and HF comparison, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide, aluminium hydroxide and positive silicic acid in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the phosphate aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(3). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 85 ℃, during sulfuric acid and fluoro-containing apatite reactor adopt, low double speed mix and blend; 400 revs/min of stirring at low speed; Middle and high speed stirs 800 and turns-1500 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. detect sulfate radical anion concentration and hydrogen fluoride in the dilute phosphoric acid slip aqueous solution in above-mentioned (one), silicon tetrafluoride content; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the sulfuric acid and fluoro-containing apatite reactor of above-mentioned (one), and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; With middle and high speed, stir, 800 revs/min-1500 revs/min of stirring velocitys, and turn-400 revs/min with stirring at low speed 300 and carry out simultaneously, churning time 120 minutes-180 minutes, stirring velocity and time are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and the comparison of HF content, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide; Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), positive silicic acid, calcium silicofluoride, magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
Embodiment:
Embodiment:
(1). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 65 ℃, hydrogen fluoride is existed in associated complex (HF) the n form with hydrogen bonded below 80 ℃, reduce the water solubility of silicon-dioxide simultaneously, do not generate silicon tetrafluoride or silicofluoric acid with silicon dioxde reaction, stop the generation of the positive silicic acid of silicon tetrafluoride hydrolysis yet; Sulfuric acid reacts in employing with fluoro-containing apatite, low double speed mix and blend, makes sulfuric acid fully contact with phosphatic rock, fully react fast; 300 revs/min of stirring at low speed; Middling speed stirs 600 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and hydrogen fluoride content in the phosphoric acid material pulp aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 100% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In phosphate aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(2). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃, 300 revs/min of rotating speeds, reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and fluorine content in the dilute phosphoric acid slip aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter; Comprise HF and SiF
4in fluorine; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 100% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and HF comparison, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide, aluminium hydroxide and positive silicic acid in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the phosphate aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
(3). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃, during sulfuric acid and fluoro-containing apatite reactor adopt, low double speed mix and blend; 300 revs/min of stirring at low speed; Middle and high speed stirs 800 revs/min-1500 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. detect sulfate radical anion concentration and hydrogen fluoride in the dilute phosphoric acid slip aqueous solution in above-mentioned (one), silicon tetrafluoride content; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to 100% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the sulfuric acid and fluoro-containing apatite reactor of above-mentioned (one), and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; With middle and high speed, stir, 800 revs/min-1500 revs/min of stirring velocitys, and turn-400 revs/min with stirring at low speed 300 and carry out simultaneously, churning time 120 minutes-180 minutes, stirring velocity and time are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and the comparison of HF content, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide; Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction, above all identical;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), positive silicic acid, calcium silicofluoride, magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher; In the dilute phosphoric acid aqueous solution, the water-soluble phosphoric acid calcium dihydrogen of trace does not affect content and the result of use of water-soluble Vanadium Pentoxide in FLAKES in primary ammonium phosphate agricultural nitrogen, phosphorus composite fertilizer;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
Claims (1)
1. in primary ammonium phosphate industrial production, phosphoric acid desulfurization is or/and the method for defluorinate, and its feature is mainly:
(1). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 65 ℃--and 79 ℃, hydrogen fluoride is existed in associated complex (HF) the n form with hydrogen bonded below 80 ℃, reduce the water solubility of silicon-dioxide simultaneously, do not generate silicon tetrafluoride or silicofluoric acid with silicon dioxde reaction, stop the generation of the positive silicic acid of silicon tetrafluoride hydrolysis yet; Sulfuric acid reacts in employing with fluoro-containing apatite, low double speed mix and blend, makes sulfuric acid fully contact with phosphatic rock, fully react fast; Stirring at low speed 300 turns-400 revs/min; Middling speed stirs 600 and turns-800 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and hydrogen fluoride content in the phosphoric acid material pulp aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--102% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to;
Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry;
(2). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃--and 100 ℃, rotating speed 300 turns-400 revs/min, reaction, churning time 8 hours-24 hours;
Two. while detecting in above-mentioned (one) 65 ℃, sulfate radical anion concentration and fluorine content in the dilute phosphoric acid slip aqueous solution after dihydrate gypsum, silicon-dioxide and/or limonite filter; Comprise HF and SiF
4in fluorine; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the dilute phosphoric acid aqueous solution after the gypsum of above-mentioned (two) filters, and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; High-speed stirring or high-shear emulsifying stir, 1000 revs/min-3000 revs/min of stirring velocitys, and churning time 30 minutes-120 minutes, stirring velocity and churning time are inversely proportional to; This step reaction also can suitably be heated, at 65 ℃--and in 85 ℃ of temperature ranges, stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and HF comparison, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), magnesium hydroxide, ironic hydroxide, aluminium hydroxide and positive silicic acid in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher;
Eight. the phosphate aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry;
(3). one. sulfuric acid and fluoro-containing apatite temperature of reaction should be controlled at 80 ℃--and 100 ℃, during sulfuric acid and fluoro-containing apatite reactor adopt or high and low double speed mix and blend; Stirring at low speed 300 turns-400 revs/min; Middle and high speed stirs 800 revs/min-1500 revs/min, monolithic middling speed paddle length 20cm-30cm, 20 °-30 ° of paddle and horizontal plane angles, the horizontal sextant angle of paddle and paddle length are inversely proportional to, and the horizontal sextant angle of middling speed mixing speed and paddle is inversely proportional to, and the length of middling speed mixing speed and paddle is inversely proportional to, paddle is fixed on stir shaft with triangular supports, to pressing down stirring, with the parallel installation of stirring at low speed axle, the distance between stir shaft is greater than the length of middling speed paddle; Reaction, churning time 8 hours-24 hours;
Two. detect sulfate radical anion concentration and hydrogen fluoride in the dilute phosphoric acid slip aqueous solution in above-mentioned (one), silicon tetrafluoride content; Silicon tetrafluoride measures with hydrogen fluoride;
Three. with sulfate radical negative ion total mass number, calculate the total mass number of calcium sulfate, then with the total mass number of calcium in calcium sulfate, calculate the total mass number of required calcium hydroxide;
Four. with hydrogen fluoride and calcium hydroxide reaction, generate the chemical equation of Calcium Fluoride (Fluorspan) and water, calculate the total mass number of required calcium hydroxide;
Five. above-mentioned (three), (fours') calcium hydroxide total mass number is added, obtains required calcium hydroxide total mass number; Or calcium hydroxide total mass number is converted into the total mass number of calcium oxide;
Six. according to the 100%--105% of calcium hydroxide or calcium oxide total mass number in above-mentioned (five), the calcium hydroxide that this is limited the quantity of or calcium oxide add in the sulfuric acid and fluoro-containing apatite reactor of above-mentioned (one), and in the dilute phosphoric acid aqueous solution, phosphoric acid quality content should be no more than 50%; With middle and high speed, stir, 800 revs/min-1500 revs/min of stirring velocitys, and turn-400 revs/min with stirring at low speed 300 and carry out simultaneously, churning time 120 minutes-180 minutes, stirring velocity and time are inversely proportional to; Stirring velocity and temperature are inversely proportional to; In phosphate aqueous solution due to this step reaction, may contain a small amount of silicofluoric acid, so the total mass number of calcium hydroxide or calcium oxide should detect data or/and the rule of thumb data of adjacent batch products sulfate radical and the comparison of HF content, calculating according to the prior art of silicofluoric acid, calculate the total mass number in shortage of calcium hydroxide or calcium oxide, and increase the total mass number of calcium hydroxide or calcium oxide;
Calcium hydroxide of the present invention or calcium oxide several times or continuously and smoothly add reaction;
Seven. in the time of 65 ℃, water-insoluble dihydrate gypsum, Calcium Fluoride (Fluorspan), positive silicic acid, calcium silicofluoride, magnesium hydroxide, ironic hydroxide and aluminium hydroxide in above-mentioned (six) are filtered, obtain the dilute phosphoric acid aqueous solution that purity is higher;
Eight. the dilute phosphoric acid aqueous solution of above-mentioned (seven) and ammoniacal liquor or ammonium hydroxide are carried out to ammonium neutralization reaction, thickening, dry.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110042243A (en) * | 2019-03-27 | 2019-07-23 | 广东清大同科环保技术有限公司 | A method of processing head ash |
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| CN101525130A (en) * | 2009-04-10 | 2009-09-09 | 武汉工程大学 | Technique for purifying and producing industrial phosphoric acid by wet-process phosphoric acid |
| 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 |
| CN102701167A (en) * | 2012-06-13 | 2012-10-03 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Method for producing industrial ammonium dihydrogen phosphate |
| CN103318863A (en) * | 2013-05-24 | 2013-09-25 | 合肥四方磷复肥有限责任公司 | Novel acid saving technology for preparing ammonium phosphate from middle-low grade phosphate ore by slurry process |
-
2013
- 2013-11-02 CN CN201310549135.9A patent/CN103641093A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1274679A (en) * | 1999-05-25 | 2000-11-29 | 四川新威矿物质饲料有限公司 | Wet phosphoric acid defluorinating agent and defluorinating process |
| CN101525130A (en) * | 2009-04-10 | 2009-09-09 | 武汉工程大学 | Technique for purifying and producing industrial phosphoric acid by wet-process phosphoric acid |
| 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 |
| CN102701167A (en) * | 2012-06-13 | 2012-10-03 | 中化化肥有限公司重庆磷复肥工程技术研究中心 | Method for producing industrial ammonium dihydrogen phosphate |
| CN103318863A (en) * | 2013-05-24 | 2013-09-25 | 合肥四方磷复肥有限责任公司 | Novel acid saving technology for preparing ammonium phosphate from middle-low grade phosphate ore by slurry process |
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| CN110042243A (en) * | 2019-03-27 | 2019-07-23 | 广东清大同科环保技术有限公司 | A method of processing head ash |
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