CN101804974B - Method for directly preparing food-grade high-purity phosphoric acid from yellow phosphorus - Google Patents
Method for directly preparing food-grade high-purity phosphoric acid from yellow phosphorus Download PDFInfo
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- CN101804974B CN101804974B CN2010101271252A CN201010127125A CN101804974B CN 101804974 B CN101804974 B CN 101804974B CN 2010101271252 A CN2010101271252 A CN 2010101271252A CN 201010127125 A CN201010127125 A CN 201010127125A CN 101804974 B CN101804974 B CN 101804974B
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 214
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 107
- 238000000034 method Methods 0.000 title claims abstract description 42
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 137
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 230000004927 fusion Effects 0.000 claims abstract description 7
- 230000002745 absorbent Effects 0.000 claims abstract description 6
- 239000002250 absorbent Substances 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 138
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 95
- 229910052698 phosphorus Inorganic materials 0.000 claims description 92
- 239000011574 phosphorus Substances 0.000 claims description 92
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 239000007789 gas Substances 0.000 claims description 39
- 238000002485 combustion reaction Methods 0.000 claims description 34
- 239000003595 mist Substances 0.000 claims description 28
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 26
- 238000002844 melting Methods 0.000 claims description 23
- 230000004087 circulation Effects 0.000 claims description 19
- 241000282326 Felis catus Species 0.000 claims description 11
- 230000005587 bubbling Effects 0.000 claims description 10
- 229910052785 arsenic Inorganic materials 0.000 claims description 8
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 claims description 8
- FPVGTPBMTFTMRT-NSKUCRDLSA-L fast yellow Chemical compound [Na+].[Na+].C1=C(S([O-])(=O)=O)C(N)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 FPVGTPBMTFTMRT-NSKUCRDLSA-L 0.000 claims description 8
- 230000001839 systemic circulation Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 238000007872 degassing Methods 0.000 claims description 6
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 3
- 238000006477 desulfuration reaction Methods 0.000 claims description 2
- 230000023556 desulfurization Effects 0.000 claims description 2
- 229910001385 heavy metal Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 16
- 239000002994 raw material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000009102 absorption Effects 0.000 description 113
- 235000011007 phosphoric acid Nutrition 0.000 description 91
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 38
- 239000007788 liquid Substances 0.000 description 35
- 238000009413 insulation Methods 0.000 description 16
- 239000007921 spray Substances 0.000 description 16
- 230000000694 effects Effects 0.000 description 13
- 125000004122 cyclic group Chemical group 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000005864 Sulphur Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000008065 acid anhydrides Chemical class 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 150000008064 anhydrides Chemical class 0.000 description 4
- 238000003556 assay Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000005188 flotation Methods 0.000 description 4
- 239000012530 fluid Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000036571 hydration Effects 0.000 description 4
- 238000006703 hydration reaction Methods 0.000 description 4
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000009841 combustion method Methods 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- 239000012717 electrostatic precipitator Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002367 phosphate rock Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 235000007983 food acid Nutrition 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012476 oxidizable substance Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Abstract
The invention discloses a method for directly preparing food-grade high-purity phosphoric acid from yellow phosphorus, which is characterized in that second-concentrated phosphoric acid collected from a master absorption column is used as a master absorbent for gaseous phosphoric acid of the master absorption column; diluted phosphoric acid collected from an auxiliary absorption column is used as a gaseous phosphoric acid absorbent of the auxiliary absorption column and a Venturi tube, and the gaseous phosphoric acid auxiliary absorbent of the master absorption column; combusting fusing raw material yellow phosphorus and entering a combustor from the bottom of a burning tower, so that the yellow phosphorus can be conveyed more safely; and the raw material fusion and the concentrated phosphoric acid are used for removing impurities, thereby effectively ensuring the high concentration and the high purity of the phosphoric acid product. The method has the advantages of simple technological process, strong practicality, stable product quality, high product yield, energy saving, low production cost and higher economic benefit.
Description
Technical field:
The invention belongs to technical field of phosphorous chemical industry, relate to a kind of method with directly preparing food-grade high-purity phosphoric acid from yellow phosphorus.
Technical background:
Phosphoric acid is the important component part of chemical industry, is important basic chemical industry raw material.The production method of phosphoric acid is divided into two kinds of thermal phosphoric acid and phosphoric acid by wet processes.Thermal phosphoric acid is meant with the Rock Phosphate (72Min BPL) to be raw material, is processed into element phosphor earlier, again the phosphoric acid that processes with element phosphor; Phosphoric acid by wet process is meant that with Rock Phosphate (72Min BPL) and mineral acid be raw material, the phosphoric acid that directly processes.The thick product of phosphoric acid by wet process is impure more, is mainly used in production fertilizer; Thermal phosphoric acid but has advantages such as product concentration height, impurity are few, can be used for making food and PHOSPHORIC ACID TECH.GRADE product salt.The production method of thermal phosphoric acid has three kinds: method one is the perfect combustion method that water absorbs system phosphoric acid after directly burning with phosphorous furnace gas; Method two is with phosphorous furnace gas and an amount of air mixed, makes phosphorus steam and phosphine gas oxidized, then gas cyaniding product Vanadium Pentoxide in FLAKES is made phosphoric acid with the dilute phosphoric acid absorption; Method three is that the phosphorus in the phosphorous furnace gas is condensed into liquid phosphorus, generates the gas Vanadium Pentoxide in FLAKES with air combustion, and water or acid absorb the liquid phosphorus combustion method that makes phosphoric acid then.At present, adopt the liquid phosphorus combustion method to produce thermal phosphoric acid more.
Chinese patent CN200910094409.3, a kind of method of directly producing electron-level phosphoric acid with yellow phosphorus relates to the phosphoric acid production method, be to put into combustion tower through purifying pretreated industrial yellow phosphorus, through multilevel oil removal, removal of impurities, the air that control is wet, industrial yellow phosphorus is fully burnt, the gas Vanadium Pentoxide in FLAKES that produces that will burn is then sent into the absorption tower, use the pure water absorption that circulates, after the phosphoric acid concentration that absorption produces reaches 85.0%-87.0%, send into the phosphoric acid purification finishing apparatus, through the moon, positively charged ion removes, aeration, after the multi-stage filtration purifying treatment, under ten thousand grades or thousand grades of purifying air environment, purify.This technology production operation control is simple, good product quality and comparatively stable.
The production method of Chinese patent CN 200510003114.2 super high pured phosphoric acids is the production methods that are used for the super high pured phosphoric acid of microelectronics industry.It adopts electronic grade yellow phosphorus or red phosphorus as raw material, and electronic grade yellow phosphorus or red phosphorus are sent into roasting kiln, feeds simultaneously through chemical treatment and the filtering excess air of strainer, and it is fully burnt, with the gaseous state P that produces
2O
5Feed in the absorption tower, in the absorption tower, adopt pure water absorptions that circulate, after the phosphoric acid concentration of circulation absorption reaches 85.0%-87.0%, send into pan tank, be not more than under the environment that thousand grades, part are not more than hundred grades in integral body and purify.
At present, the method for producing food-grade high-purity phosphoric acid is as wet phosphoric acid purifying method for refining, the thermal phosphoric acid method of purification, crystallization legal system pure phosphoric acid, electrolytic cleaning method and ion-exchange and electroosmotic drainage etc.Above method is a raw material with industrial thermal phosphoric acid or phosphoric acid by wet process all, and the method that adopts multiple working procedure to purify is carried out, and is not that direct production obtains.The problem that exists is: production technique is too much, quality is difficult to effective control, product cost increases, economic benefit is relatively poor.
Summary of the invention
Purpose of the present invention: be in order to solve above-mentioned problems of the prior art, it is simple to aim to provide a kind of flow process, practical, and product cost is lower, the food-grade high-purity phosphoric acid of constant product quality.
Technical scheme of the present invention is:
In order to reach the purpose of foregoing invention, present method is industrial yellow phosphorus to be carried out molten phosphorus purify pre-treatment, removes water-soluble and sedimentary impurity; Air carries out multilevel oil removal, removal of impurities, control wet treatment; Use pharmaceutical chemicals such as thiophosphoric anhydride, hydrogen peroxide and multi-stage filtration purifying removal of impurities, decolouring; Use time strong phosphoric acid, dilute phosphoric acid and pure water to circulate and absorb the gas Vanadium Pentoxide in FLAKES.
The present invention is achieved in that
With the method for directly preparing food-grade high-purity phosphoric acid from yellow phosphorus, comprise molten phosphorus, burning, absorption, removal of impurities and decoloration process, it is characterized in that: adopt the gaseous state phosphoric acid master absorption agent of the inferior strong phosphoric acid of main absorption tower collection as main absorption tower; The dilute phosphoric acid that adopts the collection of secondary absorption tower is as the gaseous state phosphoric acid absorption agent of secondary absorption tower, Venturi meter and the gaseous state phosphoric acid auxiliary absorbent on main absorption tower; The incendiary molten yellow phosphorus enters combustion tower by the bottom of combustion tower.
Above-described molten phosphorus, yellow phosphorus enter the preceding fusion under 60～70 ℃ temperature after hot wash is handled only of combustion tower, and water-soluble impurity and the impurity that is deposited in bottom land are removed.
Above-described burning molten yellow phosphorus advances in the low level phosphorus-melting groove with the waterhead safe transport, the molten yellow phosphorus of having avoided will being under the high-risk status with high-pressure pump or pressurized air in the conventional production lines is transported to header tank, and then through high pressure spraying this dangerous operation link that burns.
Above-described incendiary purifies air, and is to adopt negative pressure 10000～15000P
aBlower fan suction combustion tower in.
The method of above-described removal of impurities, adopt and press 1.3 times of power shaped phosphorus pentasulfide pharmaceutical chemicalss of arsenic content, under 60～80 ℃ temperature, adopt sour pump circulation to carry out the dearsenification reaction in 20～60 minutes, then 60～80 ℃ of acid temperature, adopt the Root's blower bubbling degassing desulfurization in 30～90 minutes of supplying gas, promptly get other food grade phosphoric acid of various concentration levels.
The phosphoric acid of above-described main absorption tower and secondary absorption tower gained when red acid and yellow acid occurring, reduces and throws the phosphorus amount, according to circumstances slowly adds hydrogen peroxide at the circulation groove place then, carries out 20-30 minute systemic circulation decolouring; Back gained strong phosphoric acid is handled in removal of impurities, when red acid and yellow acid occurring, according to circumstances slowly adds hydrogen peroxide, carries out 20-30 minute systemic circulation decolouring.
The above-described described equipment that method adopted with directly preparing food-grade high-purity phosphoric acid from yellow phosphorus comprises combustion tower, absorption tower, phosphorus-melting groove, concentrated acid groove, inferior concentrated acid groove, dilute acid bath, Venturi meter, deblending slot, filter, decolouring groove, sour pump, water cooler and mist eliminator; The combustion tower hypomere connects air filter and phosphorus-melting groove, and epimere connects main absorption tower; Main absorption tower hypomere connects concentrated acid groove, inferior concentrated acid groove and secondary absorption tower, and cat head connects combustion tower and cools off sour shower nozzle; Secondary absorption tower hypomere connects dilute acid bath and Venturi meter, and cat head connects main absorption tower, the sour shower nozzle of cooling and mist eliminator; The Venturi meter hypomere connects dilute acid bath, and epimere connects mist eliminator and cools off sour shower nozzle; Dilute acid bath is connected with Venturi meter, secondary absorption tower and main absorption tower respectively with sour pump, water cooler successively again; Inferior concentrated acid groove is connected with sour pump, water cooler and main absorption tower successively; The concentrated acid groove is connected with main absorption tower and deblending slot; Filter is connected with deblending slot and decolouring groove; The decolouring groove is connected with pan tank.
The operation steps of method of the present invention is:
Molten phosphorus: the bucket outer wall water that will adorn yellow phosphorus is rinsed well, and lift up into phosphorus-melting groove by crane, and add an amount of pure water, the heating of phosphorus-melting groove chuck hot water, the interior temperature of groove reaches 60～70 ℃ makes the yellow phosphorus fusion.Water-soluble impurity is removed through hot water flotation, and liquid phosphorus flows into the phosphorus scale tank by constant phosphorus level gauge, and this device makes liquid phosphorus keep the certain phosphorus liquid level of scale tank, controls to the combustion tower phosphorus supply with waterhead and valve.The yellow phosphorus pipeline adopts hot water jacket's insulation, so that liquid phosphorus keeps fluid state.Insulation hot water is from the combustion tower chuck, under the effect of hot water potential difference, flow into phosphorus-melting groove and phosphorus scale tank chuck, enter the water of condensation pond after coming out, again hot water is squeezed into the combustion tower chuck through condensate pump, to guarantee the needs of molten phosphorus homo(io)thermism in phosphorus-melting groove and the phosphorus scale tank.
Burning: in combustion tower bottom phosphorus supply constantly, burn under the effect of air oxygen supply by liquid phosphorus under the certain waterhead condition of phosphorus scale tank for liquid phosphorus, negative pressure 10000～15000P that the Vanadium Pentoxide in FLAKES gas that burning produces causes by the afterbody blower fan
aEnter main absorption tower from cat head.Purifying air that the phosphorus burning needs regulated supply by one or more blast inlets of tower hypomere.Yellow phosphorus burning heat part is absorbed by tower wall jacket water (J.W.), and hot water is for molten phosphorus insulation usefulness, and part is taken away with the gases such as Vanadium Pentoxide in FLAKES that burning produces, and enters main absorption tower.
Absorb: the Vanadium Pentoxide in FLAKES gas that the phosphorus burning that enters from top, main absorption tower produces, absorb during by a large amount of overflow phosphoric acid following current of three sour shower nozzles spray diluted acids and tower inner top overflow groove, the hydration heat part of acid anhydrides borrows recycle acid to take away, a part is passed to jacket water (J.W.) and is taken away, and one one enters secondary absorption tower with gas.The Vanadium Pentoxide in FLAKES gas that has not absorbed from bottom, main absorption tower air outlet comes out sprays sour counter-current absorption by two the rare shower nozzles in top, secondary absorption tower, and the effect on secondary absorption tower is the same with main absorption tower, and gas enters acid mist from top of tower and absorbs demister system.Enter the concentrated acid groove from the effusive strong phosphoric acid in bottom, main absorption tower, the inferior strong phosphoric acid that does not meet concentration requirement enters time strong phosphoric acid groove, enters plate cooler by cyclic acid pump and is cooled to 45-60 ℃, supplies recycle acid to main absorption tower; Enter dilute acid bath from the effusive dilute phosphoric acid in bottom, secondary absorption tower, enter plate cooler by cyclic acid pump and be cooled to 45-60 ℃, supply recycle acid to major and minor absorption tower and Venturi meter, the Vanadium Pentoxide in FLAKES gas that has not absorbed, a part is for tower shower nozzle spray acid absorption; A part absorbs for the overflow of top, absorption tower overflow groove.
When finding that at circulation groove the outlet acid of main absorption tower and secondary absorption tower is owing to fully oxidation of phosphorus, and when red acid and yellow acid occurring, should reduce the phosphorus amount of throwing, according to circumstances slowly add a certain amount of hydrogen peroxide then at the circulation groove place, approximately through 20-30 minute systemic circulation, after complete oxidation acid colourity is normal, adjust the phosphorus amount of throwing again.The acid of strong phosphoric acid groove is sent the removal of impurities treatment trough through after the assay was approved.
Demist: the gas and the acid mist that come out from top, secondary absorption tower enter Venturi meter, the diluted acid of being stamped through the diluted acid pump by dilute acid bath absorbs at trunnion place spray, acid mist is removed acid mist through keeping off mist eliminator and silk screen carbon mist eliminator or electrostatic precipitator again, and through the blower fan emptying, diluted acid flows back to dilute acid bath.
Removal of impurities: the phosphoric acid of strong phosphoric acid groove, meet the specification of industrial phosphoric acid through check after, go out acid through the bypass acid tube of cyclic acid pump and advance the removal of impurities reactive tank, under 60～80 ℃ of situations of insulation, add 1.3 times of thiophosphoric anhydrides reactions dearsenification removal of impurities in 20～60 minutes according to arsenic content.The hot water that reactive tank chuck heat tracing is produced by combustion tower, supply with by utilidor, react completely after plate-and-frame filter press filters, remove harmful elements such as arsenic, fluorine, lead, mercury, cadmium, sulphur is removed in the bubbling degassing again, sulphur removal keeps 60～80 ℃ of the interior acid temperature of groove, and bubbling was lowered the temperature after 40～90 minutes; If sour look bad, add the further oxidative decoloration of hydrogen peroxide, it is to be packaged to squeeze into pan tank then.
The phosphoric acid quality that present method is produced is better than the requirement of GB3149-2004 food grade phosphoric acid greatly, and wherein contained phosphoric acid quality mark is up to 95～102%.
Filter residue dries after hot wash, with the lime neutralization, transports the waste tank discharging to, and the washing clear liquid returns phosphoric acid production system.
Advantage of the present invention and positively effect:
1, described method with directly preparing food-grade high-purity phosphoric acid from yellow phosphorus, be to adopt the gaseous state phosphoric acid master absorption agent of the inferior strong phosphoric acid of main absorption tower collection as main absorption tower, the dilute phosphoric acid that adopts the collection of secondary absorption tower has guaranteed high-purity phosphoric acid product high density effectively as the gaseous state phosphoric acid absorption agent of secondary absorption tower and Venturi meter and the gaseous state phosphoric acid auxiliary absorbent on main absorption tower.
2, burning fused raw material yellow phosphorus of the present invention enters the combustion chamber by the bottom of combustion tower, in the low level phosphorus-melting groove with the waterhead safe transport, the molten yellow phosphorus of having avoided will being under the high-risk status with high-pressure pump or pressurized air in the conventional production lines is transported to header tank, and then through high pressure spraying this dangerous operation link that burns.
3, present method adopts raw materials melt and the multiple removal of impurities of strong phosphoric acid, has guaranteed the high purity of phosphoric acid product effectively, reaches the quality products of food grade.
4, the technical process of the inventive method is simple, practical, output and yield height, constant product quality, production cost is lower, save energy, power consumption only is 50% of a traditional technology, and total system need not fire coal and steam boiler, and better economic benefit is the good method with directly preparing food-grade high-purity phosphoric acid from yellow phosphorus.
Description of drawings:
Fig. 1: technological process of production synoptic diagram.
Embodiment:
Below in conjunction with drawings and Examples, the invention will be further described.
Embodiment 1:
The bucket outer wall water of dress yellow phosphorus is rinsed well, lifted up into phosphorus-melting groove by crane, and add an amount of pure water, the heating of phosphorus-melting groove chuck hot water, the interior temperature of groove reaches 65 ℃ makes the yellow phosphorus fusion.Water-soluble impurity is removed through hot water flotation, and liquid phosphorus flows into the phosphorus scale tank by constant phosphorus level gauge, and this device makes liquid phosphorus keep the certain phosphorus liquid level of scale tank, controls to the combustion tower phosphorus supply with waterhead and valve.The yellow phosphorus pipeline adopts hot water jacket's insulation, so that liquid phosphorus keeps fluid state.Insulation hot water is from the combustion tower chuck, under the effect of hot water potential difference, flow into phosphorus-melting groove and phosphorus scale tank chuck, enter the water of condensation pond after coming out, again water is squeezed into the tower chuck through condensate pump, with the hot water that guarantees that molten phosphorus homo(io)thermism needs in phosphorus-melting groove and the phosphorus scale tank.
In the phosphorus supply constantly of combustion tower bottom, burn under the effect of air oxygen supply by liquid phosphorus under the certain waterhead condition of phosphorus scale tank for liquid phosphorus, the negative pressure 11000P that causes by the afterbody blower fan
aEnter main absorption tower from cat head.Purifying air that the phosphorus burning needs regulated supply by the blast inlet of tower hypomere both sides.Yellow phosphorus burning heat part is absorbed by tower wall jacket water (J.W.), and hot water is used for molten phosphorus insulation; The P that part produces with burning
2O
5Take away Deng gas, enter main absorption tower.
The Vanadium Pentoxide in FLAKES gas that the phosphorus burning that enters from top, main absorption tower produces, absorb during by a large amount of overflow phosphoric acid following current of three sour shower nozzles spray diluted acids and tower inner top overflow groove, the hydration heat part of acid anhydrides borrows recycle acid to take away, a part is passed to jacket water (J.W.) and is taken away, and a part enters secondary absorption tower with gas.The Vanadium Pentoxide in FLAKES gas that has not absorbed from bottom, main absorption tower air outlet comes out sprays sour counter-current absorption by two the rare shower nozzles in top, secondary absorption tower, and the effect on secondary absorption tower is the same with main absorption tower, and gas enters acid mist absorption demister system from paying top of tower.Enter the concentrated acid groove from the effusive strong phosphoric acid in bottom, main absorption tower; Enter time strong phosphoric acid groove from effusive the strong phosphoric acid in bottom, main absorption tower, enter plate cooler by cyclic acid pump and be cooled to 45 ℃, supply recycle acid to main absorption tower; Enter dilute acid bath from the effusive dilute phosphoric acid in bottom, secondary absorption tower, enter plate cooler by cyclic acid pump and be cooled to 45 ℃, supply recycle acid to major and minor absorption tower and Venturi meter, the Vanadium Pentoxide in FLAKES gas that has not absorbed, a part is for tower shower nozzle spray acid absorption; Overflow for top, absorption tower overflow groove absorbs.
When finding that at circulation groove the outlet acid of main absorption tower and secondary absorption tower is owing to fully oxidation of phosphorus, and when red acid and yellow acid occurring, should reduce the phosphorus amount of throwing, according to circumstances slowly add a certain amount of hydrogen peroxide then at the circulation groove place, approximately through 20-30 minute systemic circulation, after complete oxidation acid colourity is normal, adjust the phosphorus amount of throwing again.The acid of circulation acid tank is sent the removal of impurities treatment trough through after the assay was approved.
The gas and the acid mist that come out from top, secondary absorption tower enter Venturi meter, and the diluted acid of being stamped through the diluted acid pump by dilute acid bath absorbs at trunnion place spray, and acid mist is through keeping off mist eliminator again and silk screen carbon mist eliminator is removed acid mist, and through the blower fan emptying, diluted acid flows back to dilute acid bath.
The phosphoric acid of circulation acid tank, meet the specification of industrial phosphoric acid through check after, go out acid through the bypass acid tube of cyclic acid pump and advance the dearsenification reactive tank, under 60 ℃ of situations of insulation, add 1.3 times of thiophosphoric anhydrides reactions dearsenification in 30 minutes according to arsenic content.The hot water that reactive tank chuck heat tracing is produced by combustion tower is supplied with by utilidor, reacts completely after plate-and-frame filter press filtration back clear liquid enters the decolouring groove, and sulphur is removed in the bubbling degassing, keeps 60 ℃ of the interior acid temperature of groove, and bubbling was lowered the temperature after 40 minutes; If sour look bad, add the further oxidative decoloration of hydrogen peroxide, it is to be packaged to squeeze into pan tank then.
Embodiment 2:
The bucket outer wall water of dress yellow phosphorus is rinsed well, lifted up into phosphorus-melting groove by crane, and add an amount of pure water, the heating of phosphorus-melting groove chuck hot water, the interior temperature of groove reaches 65 ℃ makes the yellow phosphorus fusion.Water-soluble impurity is removed through hot water flotation, and liquid phosphorus flows into the phosphorus scale tank by constant phosphorus level gauge, and this device makes liquid phosphorus keep the certain phosphorus liquid level of scale tank, controls to the combustion tower phosphorus supply with waterhead and valve.The yellow phosphorus pipeline adopts hot water jacket's insulation, so that liquid phosphorus keeps fluid state.Insulation hot water is from the bottom of burning cat head tank, hot water flows into phosphorus-melting groove and phosphorus scale tank chuck under the effect of potential difference, enter the water of condensation pond after coming out, again hot water is squeezed into the tower chuck through condensate pump, with the hot water that guarantees that molten phosphorus homo(io)thermism needs in phosphorus-melting groove and the phosphorus scale tank.
In the phosphorus supply constantly of combustion tower bottom, burn under the effect of air oxygen supply by liquid phosphorus under the certain waterhead condition of phosphorus scale tank for liquid phosphorus, the negative pressure 13000P that causes by the afterbody blower fan
aEnter main absorption tower from cat head.Purifying air that the phosphorus burning needs regulated supply by two blast inlets of tower hypomere both sides.Yellow phosphorus burning heat part is absorbed by tower wall jacket water (J.W.), and part is absorbed by cat head, and hot water is used for molten phosphorus insulation; Part is taken away with the gases such as Vanadium Pentoxide in FLAKES that burning produces, and enters main absorption tower.
The Vanadium Pentoxide in FLAKES gas that the phosphorus burning that enters from top, main absorption tower produces, absorb during by a large amount of overflow phosphoric acid following current of three sour shower nozzles spray diluted acids and tower inner top overflow groove, the hydration heat part of acid anhydrides borrows recycle acid to take away, a part is passed to jacket water (J.W.) and is taken away, and one one enters secondary absorption tower with gas.The Vanadium Pentoxide in FLAKES gas that has not absorbed from bottom, main absorption tower air outlet comes out sprays sour counter-current absorption by two the rare shower nozzles in top, secondary absorption tower, and the effect on secondary absorption tower is the same with main absorption tower, and gas enters acid mist and absorbs demister system from top, secondary absorption tower.Enter the concentrated acid groove from the effusive strong phosphoric acid in bottom, main absorption tower; Enter time strong phosphoric acid groove from effusive the strong phosphoric acid in bottom, main absorption tower, enter plate cooler by cyclic acid pump and be cooled to 50 ℃, supply recycle acid to main absorption tower; Enter dilute acid bath from the effusive dilute phosphoric acid in bottom, secondary absorption tower, enter plate cooler by cyclic acid pump and be cooled to 50 ℃, supply recycle acid to major and minor absorption tower and Venturi meter, the Vanadium Pentoxide in FLAKES gas that has not absorbed, a part is for tower shower nozzle spray acid absorption; A part absorbs for the overflow of top, absorption tower overflow groove.
When finding that at circulation groove the outlet acid of main absorption tower and secondary absorption tower is owing to fully oxidation of phosphorus, and when red acid and yellow acid occurring, should reduce the phosphorus amount of throwing, according to circumstances slowly add a certain amount of hydrogen peroxide then at the circulation groove place, approximately through 25 minutes systemic circulation, after complete oxidation acid colourity is normal, adjust the phosphorus amount of throwing again.The acid of circulation acid tank is sent the removal of impurities treatment trough through after the assay was approved.
The gas and the acid mist that come out from top, secondary absorption tower enter Venturi meter, and the diluted acid of being stamped through the diluted acid pump by dilute acid bath absorbs at trunnion place spray, and acid mist is removed acid mist through electrostatic precipitator, through the blower fan emptying.The diluted acid that reclaims flows back to dilute acid bath.
The phosphoric acid of circulation acid tank, meet the specification of industrial phosphoric acid through check after, go out acid through the bypass acid tube of cyclic acid pump and advance the dearsenification reactive tank, under 75 ℃ of situations of insulation, add 1.3 times of thiophosphoric anhydrides reactions dearsenification in 55 minutes according to arsenic content.The hot water that reactive tank chuck heat tracing is produced by combustion tower is supplied with by utilidor, reacts completely after plate-and-frame filter press filtration back clear liquid enters the decolouring groove, and sulphur is removed in the bubbling degassing, keeps 75 ℃ of the interior acid temperature of groove, and bubbling was lowered the temperature after 80 minutes; If sour look bad, add the further oxidative decoloration of hydrogen peroxide, it is to be packaged to squeeze into pan tank then.
Embodiment 3:
The bucket outer wall water of dress yellow phosphorus is rinsed well, lifted up into phosphorus-melting groove by crane, and add an amount of pure water, the heating of phosphorus-melting groove chuck hot water, the interior temperature of groove reaches 70 ℃ makes the yellow phosphorus fusion.Water-soluble impurity is removed through hot water flotation, and liquid phosphorus flows into the phosphorus scale tank by constant phosphorus level gauge, and this device makes liquid phosphorus keep the certain phosphorus liquid level of scale tank, controls to the combustion tower phosphorus supply with waterhead and valve.The yellow phosphorus pipeline adopts hot water jacket's insulation, so that liquid phosphorus keeps fluid state.Insulation hot water is from the combustion tower chuck, hot water flows into phosphorus-melting groove and phosphorus scale tank chuck under the effect of potential difference, enter the water of condensation pond after coming out, again hot water is squeezed into the tower chuck through condensate pump, with the hot water that guarantees that molten phosphorus homo(io)thermism needs in phosphorus-melting groove and the phosphorus scale tank.
In the phosphorus supply constantly of combustion tower bottom, burn under the effect of air oxygen supply by liquid phosphorus under the certain waterhead condition of phosphorus scale tank for liquid phosphorus, the negative pressure 10000～15000P that causes by the afterbody blower fan
aEnter main absorption tower from cat head.Purifying air that the phosphorus burning needs regulated supply by three blast inlets of tower hypomere.Yellow phosphorus burning heat part is absorbed by tower wall jacket water (J.W.), and part is absorbed by cat head, and chuck hot water is used for molten phosphorus insulation; The P that part produces with burning
2O
5Take away Deng gas, enter main absorption tower.
The Vanadium Pentoxide in FLAKES gas that the phosphorus burning that enters from top, main absorption tower produces, absorb during by a large amount of overflow phosphoric acid following current of three sour shower nozzles spray diluted acids and tower inner top overflow groove, the hydration heat part of acid anhydrides borrows recycle acid to take away, a part is passed to jacket water (J.W.) and is taken away, and one one enters secondary absorption tower with gas.The Vanadium Pentoxide in FLAKES gas that has not absorbed from bottom, main absorption tower air outlet comes out sprays sour counter-current absorption by two the rare shower nozzles in top, secondary absorption tower, and the effect on secondary absorption tower is the same with main absorption tower, and gas enters acid mist and absorbs demister system from top, secondary absorption tower.Enter the concentrated acid groove from the effusive strong phosphoric acid in bottom, main absorption tower; Enter time strong phosphoric acid groove from effusive the strong phosphoric acid in bottom, main absorption tower, enter plate cooler by cyclic acid pump and be cooled to 60 ℃, supply recycle acid to main absorption tower; Enter dilute acid bath from the effusive dilute phosphoric acid in bottom, secondary absorption tower, enter plate cooler by cyclic acid pump and be cooled to 50 ℃, supply recycle acid to major and minor absorption tower and Venturi meter, the Vanadium Pentoxide in FLAKES gas that has not absorbed, a part is for tower shower nozzle spray acid absorption; Overflow for top, absorption tower overflow groove absorbs.
When finding that at circulation groove the outlet acid of main absorption tower and secondary absorption tower is owing to fully oxidation of phosphorus, and when red acid and yellow acid occurring, should reduce the phosphorus amount of throwing, according to circumstances slowly add a certain amount of hydrogen peroxide then at the circulation groove place, approximately through 30 minutes systemic circulation, after complete oxidation acid colourity is normal, adjust the phosphorus amount of throwing again.The acid of circulation acid tank is sent the removal of impurities treatment trough through after the assay was approved.
The gas and the acid mist that come out from top, secondary absorption tower enter Venturi meter, and the diluted acid of being stamped through the diluted acid pump by dilute acid bath absorbs at trunnion place spray, and acid mist is through keeping off mist eliminator again and silk screen carbon mist eliminator is removed acid mist, and through the blower fan emptying, diluted acid flows back to dilute acid bath.
The phosphoric acid of circulation acid tank, meet the specification of industrial phosphoric acid through check after, go out acid through the bypass acid tube of cyclic acid pump and advance the dearsenification reactive tank, under 70 ℃ of situations of insulation, add 1.3 times of thiophosphoric anhydrides reactions dearsenification in 50 minutes according to arsenic content.The hot water that reactive tank chuck heat tracing is produced by combustion tower is supplied with by utilidor, reacts completely after plate-and-frame filter press filtration back clear liquid enters the decolouring groove, and sulphur is removed in the bubbling degassing, keeps 60 ℃ of the interior acid temperature of groove, and bubbling was lowered the temperature after 80 minutes; If sour look bad, add the further oxidative decoloration of hydrogen peroxide, it is to be packaged to squeeze into pan tank then.
Phosphoric acid product quality (%):
Project name GB3149-2004 embodiment 1 embodiment 2 embodiment 3
The transparent thick liquid water white transparency of appearance colorless thick liquid water white transparency thick liquid water white transparency thick liquid
Phosphoric acid (HP
4) 〉=85 102 98.6 96.3
Fluorochemical (in F)≤0.0007 0.00056 0.00058 0.00062
Readily oxidizable substance is (with H
3PO
3Meter)≤0.0020 0.00080 0.00140 0.00160
Arsenic (As)≤0.00001 0.00001 0.00001 0.00001
Heavy metal (in Pb)≤0.0005 0.00028 0.00033 0.00046
Claims (4)
1. method with directly preparing food-grade high-purity phosphoric acid from yellow phosphorus, comprise molten phosphorus, burning, absorb, removal of impurities and decoloration process, it is characterized in that: adopt the gaseous state phosphoric acid master absorption agent of the inferior strong phosphoric acid of main absorption tower collection as main absorption tower, the dilute phosphoric acid that adopts the collection of secondary absorption tower is as the gaseous state phosphoric acid absorption agent of secondary absorption tower and Venturi meter and the gaseous state phosphoric acid auxiliary absorbent on main absorption tower, the incendiary molten yellow phosphorus enters combustion tower by the bottom of combustion tower, the burning molten yellow phosphorus in the low level phosphorus-melting groove with the waterhead safe transport, yellow phosphorus enters the preceding fusion under 60～70 ℃ temperature after hot wash is handled only of combustion tower, water-soluble impurity and the impurity that is deposited in bottom land are removed, and it is to adopt the blower fan of negative pressure 10000～15000Pa to send in the combustion tower that incendiary purifies air.
2. method according to claim 1, it is characterized in that: described removal of impurities is to adopt by 1.3 times of power shaped phosphorus pentasulfide pharmaceutical chemicalss of arsenic content, under 60～80 ℃ temperature, adopt sour pump circulation to carry out dearsenification and removed heavy metal in 20～60 minutes, then 60～80 ℃ of acid temperature, adopt the Root's blower bubbling degassing desulfurization in 30～90 minutes of supplying gas.
3. method according to claim 1, it is characterized in that: the phosphoric acid of main absorption tower and secondary absorption tower gained, when red acid and yellow acid occurring, reduce and throw the phosphorus amount, according to circumstances slowly add hydrogen peroxide then, carry out 20～30 minutes systemic circulation decolouring at the circulation groove place, back gained strong phosphoric acid is handled in removal of impurities, when red acid and yellow acid occurring, according to circumstances slowly add hydrogen peroxide, carry out 20～30 minutes systemic circulation decolouring.
4. the equipment that adopted of the described method of claim 1 is characterized in that: comprise combustion tower, absorption tower, phosphorus-melting groove, concentrated acid groove, inferior concentrated acid groove, dilute acid bath, Venturi meter, deblending slot, filter, decolouring groove, sour pump, water cooler and mist eliminator; The combustion tower hypomere connects air filter and phosphorus-melting groove, epimere connects main absorption tower, main absorption tower hypomere connects the concentrated acid groove, inferior concentrated acid groove and secondary absorption tower, cat head connects combustion tower, cool off sour shower nozzle, secondary absorption tower hypomere connects dilute acid bath and Venturi meter, cat head connects main absorption tower, cool off sour shower nozzle and mist eliminator, the Venturi meter hypomere connects dilute acid bath, epimere connects mist eliminator and cools off sour shower nozzle, dilute acid bath successively with sour pump, water cooler more respectively with Venturi meter, secondary absorption tower and main absorption tower connect, inferior concentrated acid groove successively with sour pump, water cooler and main absorption tower connect, the concentrated acid groove is connected with main absorption tower and deblending slot, filter is connected with deblending slot and decolouring groove, and the decolouring groove is connected with pan tank.
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| CN103771367B (en) * | 2013-12-30 | 2016-01-27 | 广西明利化工有限公司 | A kind of stirred crystallization produces the method for electron-level phosphoric acid |
| CN103771368B (en) * | 2013-12-30 | 2016-03-02 | 广西明利化工有限公司 | A kind of baffle crystallization produces the device of electron-level phosphoric acid |
| CN103754843B (en) * | 2013-12-30 | 2015-09-16 | 广西明利化工有限公司 | A kind of baffle crystallization produces the method for electron-level phosphoric acid |
| CN103771370B (en) * | 2013-12-30 | 2016-03-02 | 广西明利化工有限公司 | The device of electron-level phosphoric acid is produced in a kind of U-tube crystallization |
| CN105271148B (en) * | 2015-11-13 | 2017-09-22 | 昆明理工大学 | A kind of thermal phosphoric acid couples process units with phosphorus pentoxide |
| CN108726499B (en) * | 2018-08-01 | 2022-10-04 | 蒋华民 | Food-grade calcium hydrophosphate and preparation method thereof |
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| CN101531354A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare polyphosphoric acid |
| CN201534774U (en) * | 2009-09-30 | 2010-07-28 | 江苏澄星磷化工股份有限公司 | Device for continuously producing high-concentration polyphosphoric acid products by one-step method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101531354A (en) * | 2009-04-22 | 2009-09-16 | 瓮福（集团）有限责任公司 | Method for using phosphoric oxide to concentrate diluted phosphoric acid to prepare polyphosphoric acid |
| CN201534774U (en) * | 2009-09-30 | 2010-07-28 | 江苏澄星磷化工股份有限公司 | Device for continuously producing high-concentration polyphosphoric acid products by one-step method |
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