CA1288578C - Method of extracting phosphorus from slime - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A method of extracting phosphorus from slime resides in treating the slime with a surfactant and/or polyamphoteric electrolyte upon heating.

Description

The present in~ention relates to the production of phosphorus and more particularly to a method of extracting phosphorus from slime.

The invention will find application in processing slimes formed as a side product in the production of phosphorus, said slimes being of different compositions and storable for - different periods of time.

A great variety of prior-art methods of extracting phosphorus from slimes is a result of a complex structure of the slimes.
Slimes are aqueous emulsions of phosphorus, said emulsions being stabilized with various emulsifiers of organic or inorganic origin, such as asphalt-resinous compounds, soot finely dispersed mineral dust.

An aggregation stability of phosphorus slimes is characterized by the dispersity of phosphorus particles, the latter being dependent on the nature of the stabilizer. To stabilize less stable phosphorus emulsions, use is made of low-molecular hydrocarbons (calcium soaps), so-called "oils".
The most stable slimes are stabilized with asphalt-resinous compounds; the higher the concentration of these compounds in the slime, the more difficult it is to extract phosphorus from slime.

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~2~;'7~3 The type of the stabilizer used depends, first of all, on the composition of the raw material being processed, the extent of its preparation, and the technoloyy of phosphorus production.

The diversity of structural elements entering into the composition of the protective layers of phosphorus particles dictates a great variety of the reagents used for destructlon of the structural elements. Among them are chlorinated hydrocarbons, carbon disulphide, pyrolysis resin, hexavalent chromium compounds in an acid medium, hydrogen peroxide in phosphoric acid.

An application of non-regenerable critical inorganic reagents in the process of phosphorus extraction from slime makes the process more expensive and contaminates the environment with toxic compounds.

Known in the art is a method of phosphorus extraction from slime by treating the slime with an organochlorine reagent in the presence of hydrogen peroxide upon heating. The mass ratio of the organic reagent and phosphorus in the slime is 8--10:1 (SU, A, 856976). The extraction of phosphorus from slime by this method is based on the extraction of organic stabilizers of the phosphorus emulsion with chlorinated hydrocarbons in the presence of an oxidizer. The use of large volumes of the extractants is the main condition for the extract-.
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tion of the abo~e ~tabilizers; this complicates thetechnological proces~ ~nd makea lt more expen~ive.
Beca~e of a partial hydroly~i~ o~ the hydro-carbons, which re~ults in the ~or~ation oP hydro-chloric acid ~nd enhance~ the corro~ion activity o~
the reaction medium, corro~ion-resi~tin~ equipment mu~t be u~ed.
: Thi~ method makes it po~ible to extract phos-phorus in high yield only ~hen poorly ~tabilized 10 phosphoru~ ~limes are proce~ed. Thi~ ~ determuned by the nature of the extracting agent.
The slimes stabilized with a~phalt-r~inous com-pound~ cannot be proces~ed by thi~ method, Brie~ Description o~ the Invention It is an obaect of the in~ention to provide a me thod of extra~ t;in~, phosphoru~ from slime, which will en~ure complete e~traction of pho~phoru3 when proce3~ing slim~ o~ any ~tabilization extent~
Said object is accompli~hed by t~t a method 20 of extracting phosphoru~ from slime by tre~ting the slime with an organic reagent upon heating is propo~-ed in which~ according to the in~ention, a ~urfact-~nt and/or polyamphoteric polyeiectrolyte ~re~ls U8-ed as the organic reagent~
; 25 ~e pro~osed method ensure~ a practically complete extractlon o~ pho~phorus ~rom ~lime~ featurin~
different stsbiliæatio~ extents and stora~ time~.

The reagent~ belng used do no~ contamina~s phospho-rus and provide ~avourable condition~ ~or purifica-~ion o~ wQs~e walter ~rom suope~ ion~. The~e reagents ~re uni~er~l with re~pect to di-~ferent type~ o~
5 slime~, eaaily available, cheap, and corrosion-in active, which simpli~ie~ con~iderably the technolo-~y of the procea~.
For m~cimum ex1;raction o* pho~phoru~ ~rom slim e~ stabilized wi th a~phalt-re~ ou~ compounds, it i~
- 10 expedient to treat said ~lime~ with a ~ur~actant 0uch a3 oxyethylated alkylphenol in amount 0.5-10 per ton o~ the slime, ~ o extract pho~pho~ from 31imes stabilized with calcium 30ap~ ( "oil3'?), it i~ pr~ferably to 15 use a~ a ~ur~actant partially neutralizsd fatty acid3 in an arnount o~ 0~5~ o o-f the ælime ma~s.
To extract pho3phoru~ :erom ~limes sthbilized with molecular-colloid emulsifiers ~ resin~), 1 t i~
desirable to use 8 polyamphoteric polyelectrolgte 20 ~uch a9 the produc t of partial hydrolisis of poly-acrylonitrile9 ~aid polyelectrolyte being taken in an amou~t o~ 10~100 g per ton of the slime.
To proce~ the ~lime~ with phosphorus content of 30-40 mas~ ~0 and ~tabilized with or~anic and ml-neral component3, it i~ expedient to u~e a mi~tureof hydroxyeth~lated ~alk~lphenol and a- produc~ o~
parti.al hydrolysi~ OI polyacrylo~itrile at their ma~ ratio o~ 1:30-100~, ' ~ ~. . .. .

~ 2~ 9~3 Detailed Deecription of' the Invention The propo~ed method i~ accomplished in the following way"
To extract pho~phoru~ from slime~ which are side products o~ phosphoru~ production, said ~limes are treated with an or~Pnic reagent. Depending on the composition of the slime, determined by the cha-racter of the etabilizer~t it i~ proposed to use a~ ~n organic reagent sur~act~nt~ (nonionogenic and anion-active) and~or a polyamphoteric poly-electrolyte.
~ he action of the organic ~ea~ents chosen i~
based on their demul~i~ying acti~ity. Having a high ad~orption activity, they replace and peptize the sta~ilizer To extract pho~phoru~ ~rom lime~ sta~ilized with calcium ~oaps (low-molecular hydrocarbon~j "oil3") 9 it is proposed to uee anion-active sur~ac-tant3 such as synthetic fatty acida partially neu-tralized with an alkali. The action of such demul-si~iers i3 based on a phase inverGion residing inthat insoluble calcium soap~ are tran~formed into soluble sodium soaps and the film from the pho~pho-25 rus particleY is removed, thereby creating ~avour-able conditions ~or the coale~cence of the particles~
- Due to their availability9 it is expedlent to use bottom re~idues remainin~ a*ter En oxidati~e treat-:. :

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ment of par~fin~ a~ sy~thetic fatty acids, ~aid re~idue~ being ~ubjec~ed to partial neutralization~
The above demul~i~ier i~ introduced into slime in an amount o~ 0.5-10~ of the ~lime ms~. To extract phoe 5 phorus from ~lime~ stabilized with "a~morin~" solid emul~i~iers (asphaltenes, asphal~-resinou~ compo-unds) with a predominant content o~ a~phaltenes, it i8 propo~ed to u~e nonionogenic ~ur~actant~ whose action i~ ba~ed on hydrophilization of the hydropho-10 bic ~urface o~ 3aid emulsifier~ with ~ub~equent tran3~ormation o~ the emulsifier~ into an aqueous phase and additional pepti~ation. A~ a re~ult, the sur-~ace of the phosphorus particle~ i8 purified and the particles coalesce into lar~e parti~les. As noniono-15 genic compounds it i~ proposed to use hYdroxyethy-lated alkylphe~ols in an amount o~ 0.5-10 g per ton of the slime being processed. To e~tract phosphorus.
~rom slimes stabilized with molecular-colloid emul-~ifier~ (re~in~) adsorbed due to their surface acti-20 ~ity on the ~urface of the pho~phorus par~icles~iti~ propos~d to use polyamphoteric polyelectrolyte~.
: The product~ of partial hydroly~i~ o~ polyacrylonit-rile taken in an amount of 100100 g per ton of the slime are recommen~ed to be used a~ polyamphoteric 25 polyelec tro lgte 8. Polyelectroly~e 8 destr Q y phospho~
rus emul~ions becau~e of ~n ad~orption ~ubstitution o~ the emulsi~ier. The polyelectrolyte molec~le i9 adsorbed on the phosphorus particlee much ~tro~er than the initial stabilizer of bhe slime, not ~a-~ 7--.

. . -~2~ 78 ~vouring, however, the forlmation of ~table filmawhose destruction re8ult~ in a coQlescence-o~ the particle~. In additionj~ the coale~cence of ths phoepho~l~ particle~ .in the ~lime i~ promoted by ~lo-5 cculation of the ~uspen~ion particle~ with lon~-chain polyelectrolyte molecules, To extract ph~ephorui from 91ime containing a ~rea~ amount o~ minlaral impurities (up to 20 mass %) and a relstively low amount o* phosphorue - 10 (up to 40 ma~s ~0), it is recommended tG u8e a mix-ture of hY.droxyethylated alkylphenol and the pro-duct of partial hydrolysi3 o~ polyacrylonitrile in a mais ratio of l:30-100.
~ An effecti~e destruction o~ ~uch ilimes by said mixture i3 due to a clearly pronounced ~y nargism ra~iding in that the ~ol~electroly~e mole--cule - cross~ ka mineral particle~, enabling the - molecules of hydro~yethylated alkylphenol to des-troy the organi-c stabilizerY and "armoring" emul- .
si~iers, tran~formung them into an ~qu~ous phase, ~ This-favour~ the coalescence of pho~phoru~ par-; ticles. The 3y~er~i~m i~ most pronounced when ~`/ the I~iagents are used at the mass ratio ~pecified above.
`~ 25 The proposed reagents ensure ma2imum ex-traction o~ phoephoru-s ~rom 31ime~ ~ith different sta~ ation extent~ and ~torage time~. In ad-di~i.on to ~h@ir main applicatio~ aa demul~ifier~, ~ 8 --.
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The proposed reagents, getting into waste water, favour the purification of waste water from suspensions due to flocculation of the colloid particles and clean pipes and equipment from slime sediments due to their hydrophilization and peptization. The proposed method does not cause contamination of the environment with toxic compounds.

Specific examples of realizing the proposed methods are given hereinbelow by way of illustration.

Example 1.

A slime containing (in mass %) phosphorus, 50; solids, 10;
and water, 40, stabilized predominantly with low-molecular hydrocarbons ("oils"), is treated to extract phosphorus. The slime (100 g) is placed into a reactor, heated to 70C, and treated upon stirring with 0.5 g of partially neutralized fatty acids (C16-C21). The process duration is 1 hour.

After the separation of the slime into a phosphorus layer and a mineral layer, the latter is washed with water from the reactor. The yield of phosphorus is 90 mass %

Example 2 A slime containing ( in mass %) phosphorus, 60; solids, 5;
and water, 35, stabilized predominantly with low-molecular hydrocarbons ("oils"), is treated to extract phosphorus. The slime (100 g) is , ' ' ' ' ' -:
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pl~ced in~o B reactor, heated to 70C, and tr~ated upon stirrin~ ~ith 3 B ~ partially neutralized ~at-~y acid~ (C16-C2~ h~ proce~s duratlo~ i~ 1 hourc : ~ter the ~eparation o~ the slime into 8 pho~phorus layer and a ~ineral l~yer, the latter i9 wa~hed with water from the reactor7 ~he yield of phosphorue is 99 . 59~.
Ex~mple 3~
~limc containing (in mass ~0) phosphorus, 40;
10 solids, 15; and water, 45, stabilized predominantly ~ith low-molecular hydxocarbons ("oil~") and a~-. . phalt-resinous compounds, i9 tr~ated to extract phosphoru~ he slime ( 100 g~ i~ placed into a re-actor, he~ted to 70C, and treated upon stirrin~
:, 15 with 5 g o~ partially neutralizèd ~atty acido (Cl~-: -C2~ h~ prOCeSB duration i8 2 hou~s. A~ter the separ~tion of the slime into 8 pho~phorus layer and a mineral la~er, the latter i9 ~a~hed with wat-- er fro~ the reao~or.
. 20 The yield of phosphoru~ is 96 m~l9~3 %.
Example 4 A ~lime containin~, ( in ma~ pho~phoruo, 57; solid~, î2; and water, 31~ ~tabilized predo-min~ntly with a~phal~re~inou~ compound~ treat-~d to extract phosphoru~. The slim~ ( 100 ~) is plac-ed into a reactor, heated to 70C, and treated upon stirring with 5 ~ of partlally neutralizad ~atty acid~ (C16-C2 ~ he proc~ss duration i~ 2 hour~c, : : ` : : `:

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After thc separation o~ the ~lime into a pho~-phorus layer and a mineral layer, the latter iB
wa~hed with ~ater fro~l the reactor.
The yield o~ phosphorus ~o 90 ~aQs %~
Example 5 A slime contalning (in ma~s %) pho~phoru~65;
~olid~ 5; and water, 30, stabili~ed predominantly with asphalt-re~inou~ compound~, i8 treated to ex-tract pho~phoru~O ~he ~lime (100 ~) i8 placed into a reactor, heated to 70C, and treated upon ~tirr-ing with 0O05 m~ of hydroxyethylated slkylphenol.
The proce~ duration i8 2 hour~. After the eepara-tion of the slime into a phosphoru~ layer and a mineral layer~ the latter i8 washed with water from the reactr-The yield o~ phosphoru~ i~ 98 ma~~xample 6 A alime containing (in mass %) pho~phorus,60;
~olid~, 8; and water, 32, stabilized predominantly with a~phalt-resinous compound~, i8 txeated to ex-tract pho~phorus. The ~lime (100 ~ placed into a reactor, heated to 70C, and treated upon ~tirr-in~ with 0.2 mg o~ hydroxyethylated alkylphenol~
~he process duratio~ i8 2 hours. After the ~epara-tion o~ the slime lnto a pho~phoru~ lager and a mineral layer9 the latter i~ wa~hed with w~ter from the reactor.

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The yield of pho~phorus i8 99. 5%.
Example 7 A slime containing (in ma~ %) pho~phorus, 55;
solids9 12; and water, 33, ~tabilized predominant-ly with asphalt-resinou~ compound~? i~ treated to extract phosphorus. The ~lime (100 ~) is placed into a reaetor, heated to 70C~ and treated upon stirring with 1 mg of hydroxyethylated al~glphenol~
The proces~ duration i9 2 hours. After the separa-tion of the ~lime into a phosphorus layer and amineral layer, the latter i~ wa~hed with water from the reactor.
The yield of phosphorus i~ 95 mas~ ~0.
Example 8 A slime containing (in mass ~) pho~phorus, 67; ~olid~7 7; and water, 26~ stabilized predomi-nan~ly with re8in9, ig treated to extrac~ phospho-rus. The ~lime (100 g) i~ placed intu a reactor9 heated to 70C~ and treated upon stirring with ~ 20 1 mg of the product o~ partial hydroly~is of poly-: acrylonitrile. The proce~3 duration i~ 1 hour. Aft-er the separatlon of the slime into a phosphoru~
layer and a mineral layer, the latter i~ washed with water from the reactor.
The yield of pho~phoru~ is 95.5%.
Example 9 A ~lime containin~ (in mass ~ pho~phorusg 67; ~olids, 7; ~nd water9 26, ~tabilized predo-:

minan~ly ~,vith resln~, i8 I,reatcd to extract pho~-phorus. The ~lime ~100 ~) i3 placed into a reactor, heated -to 70C, and treated upon ~tirring with 5 mg of the product of partial hydroly3i~ of polyacry-5 lonitrile . The proce~s duration 19 1 hour. Af terthe separation of the elims into a pho~phorus layer and a mineral layer, the latter i8 washed with wat-er ~rom the reac tor.
'rhe yield o~ phosphorue i~ ga ma~l8 ~o.
Example lO
A alime containing (in ma~ ~) phosphc,rus,67;
~olids, 7; and water, 26, stabilized predommnantIy with re~in~, i8 tre~ted to extr~ct pho~phorus. The slime ( 100 g) i9 placed into a rcactor, heated to 15 70 C, and treated upon stirrin~ with 10 g of the product o~ partial hydrolysi~ OI 'polyacrylonitrile.
~'he process dura-tion i~ 1 hour. A~ter the separa-tion o~ the slime into ~ phosphoruR -laye~ a mineral layer, the latter is washed with water from the 20 reactor. --The yield of phosphoru~ i~ 99.9 ma~ %.
E~ample ll A ~lime containing (in ma~ ~0) pho~phoru~, 50~ solids, 12; and water, 38, stabilized predom:L-25 n~,n~ly with asphalt-resinou~ compoun~s with ~ pre-~ailing content o~ re3in~ treated to extract pho~phoru~. The ~lime ( 100 ~) is placad into a re-'': , ` :` ,, . . .

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actor, heated to 70C, and treated upon stirring with 10 mg of the product of partial hydrolysis of polyacrylonitrile.
The process duration is 2 hours. After the separation of the slime into a phosphorus layer and a mineral layer, th~ latter is washed with water from the reactor.

The yield of phosphorus is 95 mass %.

Example 12 A slime containing ( in mass %) phosphorus, 40; solids, 15;
and water, 45, stabilized predominantly with asphalt-resinous compounds with a prevailing content of asphaltenes, is treated to extract phosphorus. The slime (100 g) is placed into a reactor, heated to 70C, and treated upon stirring with 6.2 mg of a mixture of-hydroxyethlated alkylphenol and the product of partial hydrolysis of polyacrylonitrile in a mass ratio of 1:30. The process duration is 2 hours. After the separation of the slime into a phosphorus layer and a mineral layer, the latter is washed with water from the reactor. The yield of phosphorus is 95.5 mass %.

Example 13 A slime containing (in mass %) phosphorus, ~5; solids, 18;
and water, 37, stabilized predominantly with asphalt-resinous compounds with a prevailing content of asphaltenes is treated to extract phosphorus. The slime (100 g) is placed into a reactor, `:

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heated to 70C, and treated upon stirring with 10.1 mg of a ~ixture of hydroxyethylated alkylphenol and the product of partial hydrolysis of polyacrylonitrile in a mass ratio of 1:100. The process duration is 2 hours. After the separation of the slime into a phosphorus layer and a mineral layer, the latter is washed with water from the reactor. The yield of phosphorus is 99 mass %.

Example 14 A slime containing (in mass %) phosphorus, 38; solids, 20;
water, 42, stabilized predominantly with asphalt-resinous compounds with a prevailing content of asphaltenes is treated to extract phosphorus. The slime (100 g) is placed into a reactor, heated to 70C, and treated upon stirring with 5.1 mg of a mixture of hydroxyethylated alkylphenol and the product of partial hydrolysis of polyacrylonitrile in a mass ratio of 1:50. The process duration is 2 hours. After the separation of the slime into a phosphorus layer and a mineral layer, the latter is washed with water from the reactor. The yield of phosphorus is 97.5 mass %.

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Claims (5)

1. A method of extracting phorphorus from slime, residing in that the slime is treated with an organic reagent upon heating, said organic reagent being selected from the group consisting of a surfactant, a polyamphoteric electrolyte, and a mixture thereof.

2. A method as claimed in claim 1, wherein as a surfactant use is made of hydroxyethylated alkylphenol in an amount of 0.5-10 g per ton of the slime.

3. A method as claimed in claim 1, wherein as a surfactant use is made of partially neutralized fatty acids in an amount of 0.5-10% of the slime mass.

4. A method as claimed in claim 1, wherein as a polyamphoteric electrolyte use is made of the product of partial hydrolysis polyacrylonitrile in an amount of 10-100 g per ton of the slime.

5. A method as claimed in claim 1, wherein as an organic reagent use is made of a mixture of hydroxyethylated alkylphenol and the product of partial hydrolysis of polyacrylonitrile in a mass ratio of 1:3-100.